Binders and materials made therewith

ABSTRACT

A curable aqueous composition is disclosed comprising a carbohydrate, a crosslinking agent, and an amine base, wherein the curable aqueous composition has a pH adjusted by the amine base. Further disclosed is a method of forming a curable aqueous solution.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/177,442, filed Jun. 9, 2016, which is a continuation of U.S.application Ser. No. 13/868,233, filed Apr. 23, 2013 (now U.S. Pat. No.9,464,207), which is a continuation of U.S. application Ser. No.12/976,379 (now abandoned), filed Dec. 22, 2010, which is a continuationof U.S. application Ser. No. 11/493,080, filed Jul. 26, 2006 (now U.S.Pat. No. 7,888,445), which claims the benefit under 35 U.S.C. §119 (e)of U.S. Provisional Application Ser. No. 60/702,456, filed Jul. 26,2005, and U.S. Provisional Application Ser. No. 60/743,071, filed Dec.22, 2005, the disclosures of which are hereby incorporated herein byreference in their entirety.

BACKGROUND

Binders are useful in fabricating materials from non or looselyassembled matter. For example, binders enable two or more surfaces tobecome united. Binders may be broadly classified into two main groups:organic and inorganic, with the organic materials being subdivided intothose of animal, vegetable, and synthetic origin. Another way ofclassifying binders is based upon the chemical nature of thesecompounds: (1) protein or protein derivatives; (2) starch, cellulose, orgums and their derivatives; (3) thermoplastic synthetic resins; (4)thermosetting synthetic resins; (5) natural resins and bitumens; (6)natural and synthetic rubbers; and (7) inorganic binders. Binders alsomay be classified according to the purpose for which they are used: (1)bonding rigid surfaces, such as, rigid plastics, and metals; and (2)bonding flexible surfaces, such as, flexible plastics and thin metallicsheets, among others.

Thermoplastic binders comprise a variety of polymerized materials suchas polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, and otherpolyvinyl resins; polystyrene resins; acrylic and methacrylic acid esterresins; cyanoacrylates; and various other synthetic resins such aspolyisobutylene polyamides, courmarone-idene products, and silicones.Such thermoplastic binders may have permanent solubility and fusibilityso that they creep under stress and soften when heated. They are usedfor the manufacturing various products, for example, tapes.

Thermosetting binders comprise a variety of phenol-aldehyde,urea-aldehyde, melamine-aldehyde, and other condensation-polymerizationmaterials like the furane and polyurethane resins. Thermosetting bindersmay be characterized by being transformed into insoluble and infusiblematerials by means of either heat or catalytic action. Bindercompositions containing phenol-, resorcinol-, urea-,melamine-formaldehyde, phenolfurfuraldehyde, and the like are used forthe bonding of textiles, plastics, rubbers, and many other materials.

As indicated above, binders are useful in fabricating materials from nonor loosely assembled matter. Accordingly, compositions capable offunctioning as a binder are desirable.

SUMMARY

Cured or uncured binders in accordance with an illustrative embodimentof the present invention may comprise one or more of the followingfeatures or combinations thereof. In addition, materials in accordancewith the present invention may comprise one or more of the followingfeatures or combinations thereof:

Initially it should be appreciated that the binders of the presentinvention may be utilized in a variety of fabrication applications toproduce or promote cohesion in a collection of non or loosely assembledmatter. A collection includes two or more components. The bindersproduce or promote cohesion in at least two of the components of thecollection. For example, subject binders are capable of holding acollection of matter together such that the matter adheres in a mannerto resist separation. The binders described herein can be utilized inthe fabrication of any material.

One potential feature of the present binders is that they areformaldehyde free. Accordingly, the materials the binders are disposedupon may also be formaldehyde free, (e.g. fiberglass). In addition, thepresent binders may have a reduced trimethylamine content as compared toother known binders.

With respect to the present binder's chemical constituents, they mayinclude ester and/or polyester compounds. The binders may include esterand/or polyester compounds in combination with a vegetable oil, such assoybean oil. Furthermore, the binders may include ester and/or polyestercompounds in combination with sodium salts of organic acids. The bindersmay include sodium salts of inorganic acids. The binders may alsoinclude potassium salts of organic acids. Moreover, the binders mayinclude potassium salts of inorganic acids. The described binders mayinclude ester and/or polyester compounds in combination with a clayadditive, such as montmorillonite.

Furthermore, the binders of the present invention may include a productof a Maillard reaction. For example, see FIG. 2. As shown in FIG. 2,Maillard reactions produce melanoidins, i.e., high molecular weight,furan ring and nitrogen-containing polymers that vary in structuredepending on the reactants and conditions of their preparation.Melanoidins display a C:N ratio, degree of unsaturation, and chemicalaromaticity that increase with temperature and time of heating. (See,Ames, J. M. in “The Maillard Browning Reaction—an update,” Chemistry andIndustry (Great Britain), 1988, 7, 558-561, the disclosure of which ishereby incorporated herein by reference). Accordingly, the subjectbinders may be made via a Maillard reaction and thus containmelanoidins. It should be appreciated that the subject binders maycontain melanoidins, or other Maillard reaction products, which productsare generated by a separate process and then simply added to thecomposition that makes up the binder. The melanoidins in the binder maybe water-insoluble. Moreover, the binders may be thermoset binders.

The Maillard reactants to produce a melanoidin may include an aminereactant reacted with a reducing-sugar carbohydrate reactant. Forexample, an ammonium salt of a monomeric polycarboxylic acid may bereacted with (i) a monosaccharide in its aldose or ketose form or (ii) apolysaccharide or (iii) with combinations thereof. In another variation,an ammonium salt of a polymeric polycarboxylic acid may be contactedwith (i) a monosaccharide in its aldose or ketose form or (ii) apolysaccharide, or (iii) with combinations thereof. In yet anothervariation, an amino acid may be contacted with (i) a monosaccharide inits aldose or ketose form, or (ii) with a polysaccharide or (iii) withcombinations thereof. Furthermore, a peptide may be contacted with (i) amonosaccharide in its aldose or ketose form or (ii) with apolysaccharide or (iii) with combinations thereof. Moreover, a proteinmay be contacted with (i) a monosaccharide in its aldose or ketose formor (ii) with a polysaccharide or (iii) with combinations thereof.

It should also be appreciated that the binders of the present inventionmay include melanoidins produced in non-sugar variants of Maillardreactions. In these reactions an amine reactant is contacted with anon-carbohydrate carbonyl reactant. In one illustrative variation, anammonium salt of a monomeric polycarboxylic acid is contacted with anon-carbohydrate carbonyl reactant such as, pyruvaldehyde, acetaldehyde,crotonaldehyde, 2-furaldehyde, quinone, ascorbic acid, or the like, orwith combinations thereof. In another variation, an ammonium salt of apolymeric polycarboxylic acid may be contacted with a non-carbohydratecarbonyl reactant such as, pyruvaldehyde, acetaldehyde, crotonaldehyde,2-furaldehyde, quinone, ascorbic acid, or the like, or with combinationsthereof. In yet another illustrative variation, an amino acid may becontacted with a non-carbohydrate carbonyl reactant such as,pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furaldehyde, quinone,ascorbic acid, or the like, or with combinations thereof. In anotherillustrative variation, a peptide may be contacted with anon-carbohydrate carbonyl reactant such as, pyruvaldehyde, acetaldehyde,crotonaldehyde, 2-furaldehyde, quinone, ascorbic acid, or the like, orwith combinations thereof. In still another illustrative variation, aprotein may contacted with a non-carbohydrate carbonyl reactant such as,pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furaldehyde, quinone,ascorbic acid, and the like, or with combinations thereof.

The melanoidins discussed herein may be generated from melanoidinreactant compounds. These reactant compounds are disposed in an aqueoussolution at an alkaline pH and therefore are not corrosive. That is, thealkaline solution prevents or inhibits the eating or wearing away of asubstance, such as metal, caused by chemical decomposition brought aboutby, for example, an acid. The reactant compounds may include areducing-sugar carbohydrate reactant and an amine reactant. In addition,the reactant compounds may include a non-carbohydrate carbonyl reactantand an amine reactant.

It should also be understood that the binders described herein may bemade from melanoidin reactant compounds themselves. That is, once theMaillard reactants are mixed, this mixture can function as a binder ofthe present invention. These binders may be utilized to fabricateuncured, formaldehyde-free matter, such as fibrous materials.

In the alternative, a binder made from the reactants of a Maillardreaction may be cured. These binders may be used to fabricate curedformaldehyde-free matter, such as, fibrous compositions. Thesecompositions are water-resistant and, as indicated above, includewater-insoluble melanoidins.

It should be appreciated that the binders described herein may be usedin manufacturing products from a collection of non or loosely assembledmatter. For example, these binders may be employed to fabricate fiberproducts. These products may be made from woven or nonwoven fibers. Thefibers can be heat-resistant or non heat-resistant fibers orcombinations thereof. In one illustrative embodiment, the binders areused to bind glass fibers to make fiberglass. In another illustrativeembodiment, the binders are used to make cellulosic compositions. Withrespect to cellulosic compositions, the binders may be used to bindcellulosic matter to fabricate, for example, wood fiber board which hasdesirable physical properties (e.g., mechanical strength).

One embodiment of the invention is directed to a method formanufacturing products from a collection of non- or loosely assembledmatter. One example of using this method is in the fabrication offiberglass. However, as indicated above this method can be utilized inthe fabrication of any material, as long as the method produces orpromotes cohesion when utilized. The method may include contacting thefibers with a thermally-curable, aqueous binder. The binder may include(i) an ammonium salt of a polycarboxylic acid reactant and (ii) areducing-sugar carbohydrate reactant. These two reactants are melanoidinreactants (i.e. these reactants produce melanoidins when reacted underconditions to initiate a Mai hard reaction.) The method can furtherinclude removing water from the binder in contact with the fibers (i.e.,the binder is dehydrated). The method can also include curing the binderin contact with the glass fibers (e.g. thermally curing the binder).

Another example of utilizing this method is in the fabrication ofcellulosic materials. The method may include contacting the cellulosicmaterial (e.g., cellulose fibers) with a thermally-curable, aqueousbinder. The binder may include (i) an ammonium salt of a polycarboxylicacid reactant and (ii) a reducing-sugar carbohydrate reactant. Asindicated above, these two reactants are melanoidin reactant compounds.The method can also include removing water from the binder in contactwith the cellulosic material. As before, the method can also includecuring the binder (e.g. thermal curing).

One way of using the binders is to bind glass fibers together such thatthey become organized into a fiberglass mat. The mat of fiberglass maybe processed to form one of several types of fiberglass materials, suchas fiberglass insulation. In one example, the fiberglass material mayhave glass fibers present in the range from about 80% to about 99% byweight. The uncured binder may function to hold the glass fiberstogether. The cured binder may function to hold the glass fiberstogether.

In addition, a fibrous product is described that includes a binder incontact with cellulose fibers, such as those in a mat of wood shavingsor sawdust. The mat may be processed to form one of several types ofwood fiber board products. In one variation, the binder is uncured. Inthis variation, the uncured binder may function to hold the cellulosicfibers together. In the alternative, the cured binder may function tohold the cellulosic fibers together.

Additional features of the present invention will become apparent tothose skilled in the art upon consideration of the following detaileddescription of illustrative embodiments exemplifying the best mode ofcarrying out the invention as presently perceived.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a number of illustrative reactants for producingmelanoidins;

FIG. 2 illustrates a Maillard reaction schematic when reacting areducing sugar with an amino compound;

FIG. 3 shows the FT-IR spectrum of an illustrative embodiment of a driedbinder of the present disclosure;

FIG. 4 shows the FT-IR spectrum of an illustrative embodiment of a curedbinder of the present disclosure;

FIG. 5 shows the 650° F. hot surface performance of a fiberglass pipeinsulation material fabricated with an illustrative embodiment of abinder of the present disclosure;

FIG. 6 shows the 1000° F. hot surface performance of a fiberglass pipeinsulation material fabricated with an illustrative embodiment of abinder of the present disclosure.

DETAILED DESCRIPTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments will herein be described indetail. It should be understood, however, that there is no intent tolimit the invention to the particular forms described, but on thecontrary, the intention is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the invention.

As used herein, the phrase “formaldehyde-free” means that a binder or amaterial that incorporates a binder liberates less than about 1 ppmformaldehyde as a result of drying and/or curing. The 1 ppm is based onthe weight of sample being measured for formaldehyde release.

Cured indicates that the binder has been exposed to conditions to so asto initiate a chemical change. Examples of these chemical changesinclude, but are not limited to, (i) covalent bonding, (ii) hydrogenbonding of binder components, and chemically cross-linking the polymersand/or oligomers in the binder. These changes may increase the binder'sdurability and solvent resistance as compared to the uncured binder.Curing a binder may result in the formation of a thermoset material.Furthermore, curing may include the generation of melanoidins. Thesemelanoidins may be generated from a Maillard reaction from melanoidinreactant compounds. In addition, a cured binder may result in anincrease in adhesion between the matter in a collection as compared toan uncured binder. Curing can be initiated by, for example, heat,electromagnetic radiation or, electron beams.

In a situation where the chemical change in the binder results in therelease of water, e.g. polymerization and cross-linking, a cure can bedetermined by the amount of water released above that would occur fromdrying alone. The techniques used to measure the amount of waterreleased during drying as compared to when a binder is cured, are wellknown in the art.

In accordance with the above paragraph, an uncured binder is one thathas not been cured.

As used herein, the term “alkaline” indicates a solution having a pHthat is greater than or equal to about 7. For example, the pH of thesolution can be less than or equal to about 10. In addition, thesolution may have a pH from about 7 to about 10, or from about 8 toabout 10, or from about 9 to about 10.

As used herein, the term “ammonium” includes, but is not limited to,⁺NH₄, ⁺NH₃R¹, and ⁺NH₂R¹R², where R¹ and R² are each independentlyselected in ⁺NH₂R¹R², and where R¹ and R² are selected from alkyl,cycloalkyl, alkenyl, cycloalkenyl, heterocyclyl, aryl, and heteroaryl.

The term “alkyl” refers to a saturated monovalent chain of carbon atoms,which may be optionally branched; the term “cycloalkyl” refers to amonovalent chain of carbon atoms, a portion of which forms a ring; theterm “alkenyl” refers to an unsaturated monovalent chain of carbon atomsincluding at least one double bond, Which may be optionally branched;the term “cycloalkenyl” refers to an unsaturated monovalent chain ofcarbon atoms, a portion of which forms a ring; the term “heterocyclyl”refers to a monovalent chain of carbon and heteroatoms, wherein theheteroatoms are selected from nitrogen, oxygen, and sulfur, a portion ofwhich, including at least one heteroatom, form a ring; the term “aryl”refers to an aromatic mono or polycyclic ring of carbon atoms, such asphenyl, naphthyl, and the like; and the term “heteroaryl” refers to anaromatic mono or polycyclic ring of carbon atoms and at least oneheteroatom selected from nitrogen, oxygen, and sulfur, such aspyridinyl, pyrimidinyl, indolyl, benzoxazolyl, and the like. It is to beunderstood that each of alkyl, cycloalkyl, alkenyl, cycloalkenyl, andheterocyclyl may be optionally substituted with independently selectedgroups such as alkyl, haloalkyl, hydroxyalkyl, aminoalkyl, carboxylicacid and derivatives thereof, including esters, amides, and nitrites,hydroxy, alkoxy, acyloxy, amino, alkyl and dialkylamino, acylamino,thio, and the like, and combinations thereof. It is further to beunderstood that each of aryl and heteroaryl may be optionallysubstituted with one or more independently selected substituents, suchas halo, hydroxy, amino, alkyl or dialkylamino, alkoxy, alkylsulfonyl,cyano, nitro, and the like.

As used herein, the term “polycarboxylic acid” indicates a dicarboxylic,tricarboxylic, tetracarboxylic, pentacarboxylic, and like monomericpolycarboxylic acids, and anhydrides, and combinations thereof, as wellas polymeric polycarboxylic acids, anhydrides, copolymers, andcombinations thereof. In one aspect, the polycarboxylic acid ammoniumsalt reactant is sufficiently non-volatile to maximize its ability toremain available for reaction with the carbohydrate reactant of aMaillard reaction (discussed below). In another aspect, thepolycarboxylic acid ammonium salt may be substituted with other chemicalfunctional groups.

Illustratively, a monomeric polycarboxylic acid may be a dicarboxylicacid, including, but not limited to, unsaturated aliphatic dicarboxylicacids, saturated aliphatic dicarboxylic acids, aromatic dicarboxylicacids, unsaturated cyclic dicarboxylic acids, saturated cyclicdicarboxylic acids, hydroxy-substituted derivatives thereof, and thelike. Or, illustratively, the polycarboxylic acid(s) itself may be atricarboxylic acid, including, but not limited to, unsaturated aliphatictricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatictricarboxylic acids, unsaturated cyclic tricarboxylic acids, saturatedcyclic tricarboxylic acids, hydroxy-substituted derivatives thereof, andthe like. It is appreciated that any such polycarboxylic acids may beoptionally substituted, such as with hydroxy, halo, alkyl, alkoxy, andthe like. In one variation, the polycarboxylic acid is the saturatedaliphatic tricarboxylic acid, citric acid. Other suitable polycarboxylicacids are contemplated to include, but are not limited to, aconiticacid, adipic acid, azelaic acid, butane tetracarboxylic acid dihydride,butane tricarboxylic acid, chlorendic acid, citraconic acid,dicyclopentadiene-maleic acid adducts, diethylenetriamine pentaaceticacid, adducts of dipentene and maleic acid, ethylenediamine tetraaceticacid (EDTA), fully maleated rosin, maleated tall-oil fatty acids,fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleatedrosin oxidized with potassium peroxide to alcohol then carboxylic acid,maleic acid, malic acid, mesaconic acid, biphenol A or bisphenol Freacted via the KOLBE-Schmidt reaction with carbon dioxide to introduce3-4 carboxyl groups, oxalic acid, phthalic acid, sebacic acid, succinicacid, tartaric acid, terephthalic acid, tetrabromophthalic acid,tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid,trimesic acid, and the like, and anhydrides, and combinations thereof.

Illustratively, a polymeric polycarboxylic acid may be an acid, forexample, polyacrylic acid, polymethacrylic acid, polymaleic acid, andlike polymeric polycarboxylic acids, copolymers thereof, anhydridesthereof, and mixtures thereof. Examples of commercially availablepolyacrylic acids include AQUASET-529 (Rohm & Haas, Philadelphia, Pa.,USA), CRITERION 2000 (Kemira, Helsinki, Finland, Europe), NF1 (H.B.Fuller, St. Paul, Minn., USA), and SOKALAN (BASF, Ludwigshafen, Germany,Europe), With respect to SOKALAN, this is a water-soluble polyacryliccopolymer of acrylic acid and maleic acid, having a molecular weight ofapproximately 4000. AQUASET-529 is a composition containing polyacrylicacid cross-linked with glycerol, also containing sodium hypophosphite asa catalyst. CRITERION′ 2000 is an acidic solution of a partial salt ofpolyacrylic acid, having a molecular weight of approximately 2000. Withrespect to NF1, this is a copolymer containing carboxylic acidfunctionality and hydroxy functionality, as well as units with neitherfunctionality; NF1 also contains chain transfer agents, such as sodiumhypophosphite or organophosphate catalysts.

Further, compositions including polymeric polycarboxylic acids are alsocontemplated to be useful in preparing the binders described herein,such as those compositions described in U.S. Pat. Nos. 5,318,990,5,661,213, 6,136,916, and 6,331,350, the disclosures of which are herebyincorporated herein by reference. In particular, in U.S. Pat. Nos.5,318,990 and 6,331,350 an aqueous solution of a polymericpolycarboxylic acid, a polyol, and a catalyst is described.

As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, the polymericpolycarboxylic acid comprises an organic polymer or oligomer containingmore than one pendant carboxy group. The polymeric polycarboxylic acidmay be a homopolymer or copolymer prepared from unsaturated carboxylicacids including, but not necessarily limited to, acrylic acid,methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamicacid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid,α,β-methyleneglutaric acid, and the like. Alternatively, the polymericpolycarboxylic acid may be prepared from unsaturated anhydridesincluding, but not necessarily limited to, maleic anhydride, itaconicanhydride, acrylic anhydride, methacrylic anhydride, and the like, aswell as mixtures thereof. Methods for polymerizing these acids andanhydrides are well-known in the chemical art. The polymericpolycarboxylic acid may additionally comprise a copolymer of one or moreof the aforementioned unsaturated carboxylic acids or anhydrides and oneor more vinyl compounds including, but not necessarily limited to,styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methylacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methylmethacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidylmethacrylate, vinyl methyl ether, vinyl acetate, and the like. Methodsfor preparing these copolymers are well-known in the art. The polymericpolycarboxylic acids may comprise homopolymers and copolymers ofpolyacrylic acid. The molecular weight of the polymeric polycarboxylicacid, and in particular polyacrylic acid polymer, may be is less than10000, less than 5000, or about 3000 or less. For example, the molecularweight may be 2000.

As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, the polyol (in acomposition including a polymeric polycarboxylic acid) contains at leasttwo hydroxyl groups. The polyol should be sufficiently nonvolatile suchthat it will substantially remain available for reaction with thepolymeric polycarboxylic acid in the composition during heating andcuring operations. The polyol may be a compound with a molecular weightless than about 1000 bearing at least two hydroxyl groups such as,ethylene glycol, glycerol, pentaerythritol, trimethylol propane,sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol,glycollated ureas, 1,4-cyclohexane diol, diethanolamine,triethanolamine, and certain reactive polyols, for example,β-hydroxyalkylamides such as, for example,bis[N,N-di(β-hydroxyethyl)]adipamide, or it may be an addition polymercontaining at least two hydroxyl groups such as, polyvinyl alcohol,partially hydrolyzed polyvinyl acetate, and homopolymers or copolymersof hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and thelike.

As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, the catalyst (ina composition including a polymeric polycarboxylic acid) is aphosphorous-containing accelerator which may be a compound with amolecular weight less than about 1000 such as, an alkali metalpolyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoricacid, and an alkyl phosphinic acid or it may be an oligomer or polymerbearing phosphorous-containing groups, for example, addition polymers ofacrylic and/or maleic acids formed in the presence of sodiumhypophosphite, addition polymers prepared from ethylenically unsaturatedmonomers in the presence of phosphorous salt chain transfer agents orterminators, and addition polymers containing acid-functional monomerresidues, for example, copolymerized phosphoethyl methacrylate, and likephosphonic acid esters, and copolymerized vinyl sulfonic acid monomers,and their salts. The phosphorous-containing accelerator may be used at alevel of from about 1% to about 40%, by weight based on the combinedweight of the polymeric polycarboxylic acid and the polyol. A level ofphosphorous-containing accelerator of from about 2.5% to about 10%, byweight based on the combined weight of the polymeric polycarboxylic acidand the polyol may be used. Examples of such catalysts include, but arenot limited to, sodium hypophosphite, sodium phosphite, potassiumphosphite, disodium pyrophosphate, tetrasodium pyrophosphate, sodiumtripolyphosphate, sodium hexametaphosphate, potassium phosphate,potassium polymetaphosphate, potassium polyphosphate, potassiumtripolyphosphate, sodium trimetaphosphate, and sodiumtetrametaphosphate, as well as mixtures thereof.

Compositions including polymeric polycarboxylic acids described in U.S.Pat. Nos. 5,661,213 and 6,136,916 that are contemplated to be useful inpreparing the binders described herein comprise an aqueous solution of apolymeric polycarboxylic acid, a polyol containing at least two hydroxylgroups, and a phosphorous-containing accelerator, wherein the ratio ofthe number of equivalents of carboxylic acid groups, to the number ofequivalents of hydroxyl groups is from about 1:0.01 to about 1:3

As disclosed in U.S. Pat. Nos. 5,661,213 and 6,136,916, the polymericpolycarboxylic acid may be, a polyester containing at least twocarboxylic acid groups or an addition polymer or oligomer containing atleast two copolymerized carboxylic acid-functional monomers. Thepolymeric polycarboxylic acid is preferably an addition polymer formedfrom at least one ethylenically unsaturated monomer. The additionpolymer may be in the form of a solution of the addition polymer in anaqueous medium such as, an alkali-soluble resin which has beensolubilized in a basic medium; in the form of an aqueous dispersion, forexample, an emulsion-polymerized dispersion; or in the form of anaqueous suspension. The addition polymer must contain at least twocarboxylic acid groups, anhydride groups, or salts thereof.Ethylenically unsaturated carboxylic acids such as, methacrylic acid,acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleicacid, itaconic acid, 2-methyl itaconic acid, methylene glutaric glutaricacid, monoalkyl maleates, and monoalkyl fumarates; ethylenicallyunsaturated anhydrides, for example, maleic anhydride, itaconicanhydride, acrylic anhydride, and methacrylic anhydride; and saltsthereof, at a level of from about 1% to 100%, by weight, based on theweight of the addition polymer, may be used. Additional ethylenicallyunsaturated monomer may include acrylic ester monomers including methylacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decylacrylate, methyl methacrylate, butyl methacrylate, isodecylmethacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, andhydroxypropyl methacrylate; acrylamide or substituted acrylamides;styrene or substituted styrenes; butadiene; vinyl acetate or other vinylesters; acrylonitrile or methacrylonitrile; and the like. The additionpolymer containing at least two carboxylic acid groups, anhydridegroups, or salts thereof may have a molecular weight from about 300 toabout 10,000,000. A molecular weight from about 1000 to about 250,000may be used. When the addition polymer is an alkali-soluble resin havinga carboxylic acid, anhydride, or salt thereof, content of from about 5%to about 30%, by weight based on the total weight of the additionpolymer, a molecular weight from about 10,000 to about 100,000 may beutilized Methods for preparing these additional polymers are well-knownin the art.

As described in U.S. Pat. Nos. 5,661,213 and 6,136,916, the polyol (in acomposition including a polymeric polycarboxylic acid) contains at leasttwo hydroxyl groups and should be sufficiently nonvolatile that itremains substantially available for reaction with the polymericpolycarboxylic acid in the composition during heating and curingoperations. The polyol may be a compound with a molecular weight lessthan about 1000 bearing at least two hydroxyl groups, for example,ethylene glycol, glycerol, pentaerythritol, trimethylol propane,sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol,glycollated ureas, 1,4-cyclohexane diol, diethanolamine,triethanolamine, and certain reactive polyols, for example,β-hydroxyalkylamides, for example,bis-[N,N-di(β-hydroxyethyl)]adipamide, bis[N,N-di(β-hydroxypropyl)]azelamide, bis[N—N-di(β-hydroxypropyl)] adipamide,bis[N—N-di(β-hydroxypropyl)] glutaramide, bis[N—N-di(β-hydroxypropyl)]succinamide, and bis[N-methyl-N-(β-hydroxyethyl)] oxamide, or it may bean addition polymer containing at least two hydroxyl groups such as,polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, andhomopolymers or copolymers of hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate, and the like.

As described in U.S. Pat. Nos. 5,661,213 and 6,136,916, thephosphorous-containing accelerator (in a composition including apolymeric polycarboxylic acid) may be a compound with a molecular weightless than about 1000 such as, an alkali metal hypophosphite salt, analkali metal phosphite, an alkali metal polyphosphate, an alkali metaldihydrogen phosphate, a polyphosphoric acid, and an alkyl phosphinicacid or it may be an oligomer or polymer bearing phosphorous-containinggroups such as, addition polymers of acrylic and/or maleic acids formedin the presence of sodium hypophosphite, addition polymers prepared fromethylenically unsaturated monomers in the presence of phosphorous saltchain transfer agents or terminators, and addition polymers containingacid-functional monomer residues such as, copolymerized phosphoethylmethacrylate, and like phosphonic acid esters, and copolymerized vinylsulfonic acid monomers, and their salts. The phosphorous-containingaccelerator may be used at a level of from about 1% to about 40%, byweight based on the combined weight of the polyacid and the polyol. Alevel of phosphorous-containing accelerator of from about 2.5% to about10%, by weight based on the combined weight of the polyacid and thepolyol, may be utilized.

As used herein, the term “amine base” includes, but is not limited to,ammonia, a primary amine, i.e., NH₂R¹, and a secondary amine, i.e.,NHR¹R², where R¹ and R² are each independently selected in NHR¹R², andwhere R¹ and R² are selected from alkyl, cycloalkyl, alkenyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl, as defined herein.Illustratively, the amine base may be substantially volatile orsubstantially non-volatile under conditions sufficient to promoteformation of the thermoset binder during thermal curing. Illustratively,the amine base may be a substantially volatile base, such as, ammonia,ethylamine, diethylamine, dimethylamine, and ethylpropylamine.Alternatively, the amine base may be a substantially non-volatile base,for example, aniline, 1-naphthylamine, 2-naphthylamine, andpara-aminophenol.

As used herein, “reducing sugar” indicates one or more sugars thatcontain aldehyde groups, or that can isomerize, i.e., tautomerize, tocontain aldehyde groups, which groups are reactive with an amino groupunder Maillard reaction conditions and which groups may be oxidizedwith, for example, Cu⁺² to afford carboxylic acids. It is alsoappreciated that any such carbohydrate reactant may be optionallysubstituted, such as with hydroxy, halo, alkyl, alkoxy, and the like. Itis further appreciated that in any such carbohydrate reactant, one ormore chiral centers are present, and that both possible optical isomersat each chiral center are contemplated to be included in the inventiondescribed herein. Further, it is also to be understood that variousmixtures, including racemic mixtures, or other diastereomeric mixturesof the various optical isomers of any such carbohydrate reactant, aswell as various geometric isomers thereof, may be used in one or moreembodiments described herein.

As used herein, the term “fiberglass,” indicates heat-resistant fiberssuitable for withstanding elevated temperatures. Examples of such fibersinclude, but are not limited to, mineral fibers, aramid fibers, ceramicfibers, metal fibers, carbon fibers, polyimide fibers, certain polyesterfibers, rayon fibers, and glass fibers. Illustratively, such fibers aresubstantially unaffected by exposure to temperatures above about 120° C.

FIG. 1 shows examples of reactants for a Maillard reaction. Examples ofamine reactants include proteins, peptides, amino acids, ammonium saltsof polymeric polycarboxylic acids, and ammonium salts of monomericpolycarboxylic acids. As illustrated, “ammonium” can be [⁺H₄]_(x),[⁺NH₃R¹R²]_(x), and [⁺NH₂R¹R²]_(x), where x is at least about 1. Withrespect to ⁺NH₂R¹R², R¹ and R² are each independently selected.Moreover, R¹ and R² are selected from alkyl, cycloalkyl, alkenyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl, as described above.FIG. 1 also illustrates examples of reducing-sugar reactants forproducing melanoidins, including monosaccharides, in their aldose orketose form, polysaccharides, or combinations thereof. Illustrativenon-carbohydrate carbonyl reactants for producing melanoidins are alsoshown in FIG. 1 and include various aldehydes, e.g., pyruvaldehyde andfurfural, as well as compounds such as ascorbic acid and quinone.

FIG. 2 shows a schematic of a Maillard reaction, which culminates in theproduction of melanoidins. In its initial phase, a Maillard reactioninvolves a carbohydrate reactant, for example, a reducing sugar (notethat the carbohydrate reactant may come from a substance capable ofproducing a reducing sugar under Maillard reaction conditions). Thereaction also involves condensing the carbohydrate reactant (e.g.,reducing sugar) with an amine reactant, i.e., a compound possessing anamino group. In other words, the carbohydrate reactant and the aminereactant are the melanoidin reactants for a Maillard reaction. Thecondensation of these two constituents produces an N-substitutedglycosylamine. For a more detailed description of the Maillard reactionsee, Hodge, J. E. Chemistry of Browning Reactions in Model Systems J.Agric. Food Chem. 1953, 1, 928-943, the disclosure of which is herebyincorporated herein by reference. The compound possessing a free aminogroup in a Maillard reaction may be present in the form of an aminoacid. The free amino group can also come from a protein where the freeamino groups are available in the form of for example, the g-amino groupof lysine residues, and/or the α-amino group of the terminal amino acid.

Another aspect of conducting a Maillard reaction as described herein isthat, initially, the aqueous Maillard reactant solution (which also is abinder), as described above, has an alkaline pH. However, once thesolution is disposed on a collection of non or loosely assembled matter,and curing is initiated, the pH decreases (i.e., the binder becomesacidic). It should be understood that when fabricating a material, theamount of contact between the binder and components of machinery used inthe fabrication is greater prior to curing, (i.e., when the bindersolution is alkaline) as compared to after the binder is cured (i.e.when the binder is acidic). An alkaline composition is less corrosivethan an acidic composition. Accordingly, corrosivity of the fabricationprocess is decreased.

It should be appreciated that by using the aqueous Maillard reactantsolution described herein, the machinery used to fabricate fiberglass isnot exposed as much to an acidic solution because, as described above,the pH of the Maillard reactant solution is alkaline. Furthermore,during the fabrication the only time an acidic condition develops isafter the binder has been applied to glass fibers. Once the binder isapplied to the glass fibers, the binder and the material thatincorporates the binder, has relatively infrequent contacts with thecomponents of the machinery as compared to the time prior to applyingthe binder to the glass fibers. Accordingly, corrosivity of fiberglassfabrication (and the fabrication of other materials) is decreased.

Without being bound to theory, covalent reaction of the polycarboxylicacid ammonium salt and reducing sugar reactants of a Maillard reaction,which as described herein occurs substantially during thermal curing toproduce brown-colored nitrogenous polymeric and co-polymeric melanoidinsof varying structure, is thought to involve initial Maillard reaction ofammonia with the aldehyde moiety of a reducing-sugar carbohydratereactant to afford N-substituted glycosylamine, as shown in FIG. 2.Consumption of ammonia in such a way, with ammonia and a reducing-sugarcarbohydrate reactant combination functioning as a latent acid catalyst,would be expected to result in a decrease in pH, which decrease isbelieved to promote esterification processes and/or dehydration of thepolycarboxylic acid to afford its corresponding anhydride derivative. AtpH≦7, the Amadori rearrangement product of N-substituted glycosylamine,i.e., 1-amino-1-deoxy-2-ketose, would be expected to undergo mainly1,2-enolization with the formation of furfural when, for example,pentoses are involved, or hydroxymethylfurfural when, for example,hexoses are involved, as a prelude to melanoidin production.Concurrently, contemporaneously, or sequentially with the production ofmelanoidins, esterification processes may occur involving melanoidins,polycarboxylic acid and/or its corresponding anhydride derivative, andresidual carbohydrate, which processes lead to extensive cross-linking.Accompanied by sugar dehydration reactions, whereupon conjugated doublebonds are produced that may undergo polymerization, a water-resistantthermoset binder is produced consisting of polyester adductsinterconnected by a network of carbon-carbon single bonds. Consistentwith the above reaction scenario is a strong absorbance near 1734 cm⁻¹in the FT-IR spectrum of a cured binder described herein, whichabsorbance is within the 1750-1730 cm⁻¹ range expected for estercarbonyl C—O vibrations. The afore-mentioned spectrum is shown in FIG.4.

The following discussion is directed to (i) examples of carbohydrate andamine reactants, which can be used in a Maillard reaction and (ii) howthese reactants can be combined. First, it should be understood that anycarbohydrate and/or compound possessing a primary or secondary aminogroup, that will act as a reactant in a Maillard reaction, can beutilized in the binders of the present invention. Such compounds can beidentified and utilized by one of ordinary skill in the art with theguidelines disclosed herein.

With respect to exemplary reactants, it should also be appreciated thatusing an ammonium salt of a polycarboxylic acid as an amine reactant isan effective reactant in a Maillard reaction. Ammonium salts ofpolycarboxylic acids can be generated by neutralizing the acid groupswith an amine base, thereby producing polycarboxylic acid ammonium saltgroups. Complete neutralization, i.e., about 100% calculated on anequivalents basis, may eliminate any need to titrate or partiallyneutralize acid groups in the polycarboxylic acid(s) prior to binderformation. However, it is expected that less-than-completeneutralization would not inhibit formation of the binder. Note thatneutralization of the acid groups of the polycarboxylic acid(s) may becarried out either before or after the polycarboxylic acid(s) is mixedwith the carbohydrate(s).

With respect to the carbohydrate reactant, it may include one or morereactants having one or more reducing sugars. In one aspect, anycarbohydrate reactant should be sufficiently nonvolatile to maximize itsability to remain available for reaction with the polycarboxylic acidammonium salt reactant. The carbohydrate reactant may be amonosaccharide in its aldose or ketose form, including a triose, atetrose, a pentose, a hexose, or a heptose; or a polysaccharide; orcombinations thereof. A carbohydrate reactant may be a reducing sugar,or one that yields one or more reducing sugars in situ under thermalcuring conditions. For example, when a triose serves as the carbohydratereactant, or is used in combination with other reducing sugars and/or apolysaccharide, an aldotriose sugar or a ketotriose sugar may beutilized, such as glyceraldehyde and dihydroxyacetone, respectively.When a tetrose serves as the carbohydrate reactant, or is used incombination with other reducing sugars and/or a polysaccharide,aldotetrose sugars, such as erythrose and threose; and ketotetrosesugars, such as erythrulose, may be utilized. When a pentose serves asthe carbohydrate reactant, or is used in combination with other reducingsugars and/or a polysaccharide, aldopentose sugars, such as ribose,arabinose, xylose, and lyxose; and ketopentose sugars, such as ribulose,arabulose, xylulose, and lyxulose, may be utilized. When a hexose servesas the carbohydrate reactant, or is used in combination with otherreducing sugars and/or a polysaccharide, aldohexose sugars, such asglucose (i.e., dextrose), mannose, galactose, allose, altrose, talose,gulose, and idose; and ketohexose sugars, such as fructose, psicose,sorbose and tagatose, may be utilized. When a heptose serves as thecarbohydrate reactant, or is used in combination with other reducingsugars and/or a polysaccharide, a ketoheptose sugar such assedoheptulose may be utilized. Other stereoisomers of such carbohydratereactants not known to occur naturally are also contemplated to beuseful in preparing the binder compositions as described herein. When apolysaccharide serves as the carbohydrate, or is used in combinationwith monosaccharides, sucrose, lactose, maltose, starch, and cellulosemay be utilized.

Furthermore, the carbohydrate reactant in the Maillard reaction may beused in combination with a non-carbohydrate polyhydroxy reactant.Examples of non-carbohydrate polyhydroxy reactants which can be used incombination with the carbohydrate reactant include, but are not limitedto, trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol,partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinylacetate, and mixtures thereof. In one aspect, the non-carbohydratepolyhydroxy reactant is sufficiently nonvolatile to maximize its abilityto remain available for reaction with a monomeric or polymericpolycarboxylic acid reactant. It is appreciated that the hydrophobicityof the non-carbohydrate polyhydroxy reactant may be a factor indetermining the physical properties of a binder prepared as describedherein.

When a partially hydrolyzed polyvinyl acetate serves as anon-carbohydrate polyhydroxy reactant, a commercially available compoundsuch as an 87-89% hydrolyzed polyvinyl acetate may be utilized, such as,DuPont ELVANOL 51-05. DuPont ELVANOL 51-05 has a molecular weight ofabout 22,000-26,000 Da and a viscosity of about 5.0-6.0 centipoises.Other partially hydrolyzed polyvinyl acetates contemplated to be usefulin preparing binder compositions as described herein include, but arenot limited to, 87-89% hydrolyzed polyvinyl acetates differing inmolecular weight and viscosity from ELVANOL 51-05, such as, for example,DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22,ELVANOL 50-26, ELVANOL 50-42; and partially hydrolyzed polyvinylacetates differing in molecular weight, viscosity, and/or degree ofhydrolysis from ELVANOL 51-05, such as, DuPont ELVANOL 51-03 (86-89%hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydrolyzed), ELVANOL 70-27(95.5-96.5% hydrolyzed), ELVANOL 60-30 (90-93% hydrolyzed). Otherpartially hydrolyzed polyvinyl acetates contemplated to be useful inpreparing binder compositions as described herein include, but are notlimited to, Clariant MOWIOL 15-79, MOWIOL 3-83, MOWIOL 4-88, MOWIOL5-88, MOWIOL 8-88, MOWIOL 18-88, MOWIOL 23-88, MOWIOL 26-88, MOWIOL40-88, MOWIOL 47-88, and MOWIOL 30-92, as well as Celanese CELVOL 203,CELVOL 205, CELVOL 502, CELVOL 504, CELVOL 513, CELVOL 523, CELVOL523TV, CELVOL 530, CELVOL 540, CELVOL 540TV, CELVOL 418, CELVOL 425, andCELVOL 443. Also contemplated to be useful are similar or analogouspartially hydrolyzed polyvinyl acetates available from other commercialsuppliers.

When a fully hydrolyzed polyvinyl acetate serves as a non-carbohydratepolyhydroxy reactant, Clariant MOWIOL 4-98, having a molecular weight ofabout 27,000 Da, may be utilized. Other fully hydrolyzed polyvinylacetates contemplated to be useful include, but are not limited to,DuPont ELVANOL 70-03 (98.0-98.8% hydrolyzed), ELVANOL 70-04 (98.0-98.8%hydrolyzed), ELVANOL 70-06 (98.5-99.2% hydrolyzed), ELVANOL 90-50(99.0-99.8% hydrolyzed), ELVANOL 70-20 (98.5-99.2% hydrolyzed), ELVANOL70-30 (98.5-99.2% hydrolyzed), ELVANOL 71-30 (99.0-99.8% hydrolyzed),ELVANOL 70-62 (98.4-99.8% hydrolyzed), ELVANOL 70-63 (98.5-99.2%hydrolyzed), ELVANOL 70-75 (98.5-99.2% hydrolyzed), Clariant MOWIOL3-98, MOWIOL 6-98, MOWIOL 10-98, MOWIOL 20-98, MOWIOL 56-98, MOWIOL28-99, and Celanese CELVOL 103, CELVOL 107, CELVOL 305, CELVOL 310,CELVOL 325, CELVOL 325LA, and CELVOL 350, as well as similar oranalogous fully hydrolyzed polyvinyl acetates from other commercialsuppliers.

The aforementioned Maillard reactants may be combined to make an aqueouscomposition that includes a carbohydrate reactant and an amine reactant.These aqueous binders represent examples of uncured binders. Asdiscussed below, these aqueous compositions can be used as binders ofthe present invention. These binders are formaldehyde-free, curable,alkaline, aqueous binder compositions. Furthermore, as indicated above,the carbohydrate reactant of the Maillard reactants may be used incombination with a non-carbohydrate polyhydroxy reactant. Accordingly,any time the carbohydrate reactant is mentioned it should be understoodthat it can be used in combination with a non-carbohydrate polyhydroxyreactant.

In one illustrative embodiment, the aqueous solution of Maillardreactants may include (i) an ammonium salt of one or more polycarboxylicacid reactants and (ii) one or more carbohydrate reactants having areducing sugar. The pH of this solution prior to placing it in contactwith the material to be bound can be greater than or equal to about 7.In addition, this solution can have a pH of less than or equal to about10. The ratio of the number of moles of the polycarboxylic acidreactant(s) to the number of moles of the carbohydrate reactant(s) canbe in the range from about 1:4 to about 1:15. In one example, the ratioof the number of moles of the polycarboxylic acid reactant(s) to thenumber of moles of the carbohydrate reactant(s) in the bindercomposition is about 1:5. In another example, the ratio of the number ofmoles of the polycarboxylic acid reactant(s) to the number of moles ofthe carbohydrate reactant(s) is about 1:6. In yet another example, theratio of the number of moles of the polycarboxylic acid reactant(s) tothe number of moles of the carbohydrate reactant(s) is about 1:7.

As described above, the aqueous binder composition includes (i) anammonium salt of one or more polycarboxylic acid reactants and (ii) oneor more carbohydrate reactants having a reducing sugar. It should beappreciated that when an ammonium salt of a monomeric or a polymericpolycarboxylic acid is used as an amine reactant, the molar equivalentsof ammonium ion may or may not be equal to the molar equivalents of acidsalt groups present on the polycarboxylic acid. In one illustrativeexample, an ammonium salt may be monobasic, dibasic, or tribasic when atricarboxylic acid is used as a polycarboxylic acid reactant. Thus, themolar equivalents of the ammonium ion may be present in an amount lessthan or about equal to the molar equivalents of acid salt groups presentin a polycarboxylic acid. Accordingly, the salt can be monobasic ordibasic when the polycarboxylic acid reactant is a dicarboxylic acid.Further, the molar equivalents of ammonium ion may be present in anamount less than, or about equal to, the molar equivalents of acid saltgroups present in a polymeric polycarboxylic acid, and so on and soforth. When a monobasic salt of a dicarboxylic acid is used, or when adibasic salt of a tricarboxylic acid is used, or when the molarequivalents of ammonium ions are present in an amount less than themolar equivalents of acid salt groups present in a polymericpolycarboxylic acid, the pH of the binder composition may requireadjustment to achieve alkalinity.

The uncured, formaldehyde-free, thermally-curable, alkaline, aqueousbinder composition can be used to fabricate a number of differentmaterials. In particular, these binders can be used to produce orpromote cohesion in non or loosely assembled matter by placing thebinder in contact with the matter to be bound. Any number of well knowntechniques can be employed to place the aqueous binder in contact withthe material to be bound. For example, the aqueous binder can be sprayedon (for example during the binding glass fibers) or applied via aroll-coat apparatus.

These aqueous binders can be applied to a mat of glass fibers (e.g.,sprayed onto the mat), during production of fiberglass insulationproducts. Once the aqueous binder is in contact with the glass fibersthe residual heat from the glass fibers (note that the glass fibers aremade from molten glass and thus contain residual heat) and the flow ofair through the fibrous mat will evaporate (i.e., remove) water from thebinder. Removing the water leaves the remaining components of the binderon the fibers as a coating of viscous or semi-viscous high-solidsliquid. This coating of viscous or semi-viscous high-solids liquidfunctions as a binder. At this point, the mat has not been cured. Inother words, the uncured binder functions to bind the glass fibers inthe mat.

Furthermore, it should be understood that the above described aqueousbinders can be cured. For example, any of the above described aqueousbinders can be disposed (e.g., sprayed) on the material to be bound, andthen heated. For example, in the case of making fiberglass insulationproducts, after the aqueous binder has been applied to the mat, thebinder coated mat is transferred to a curing oven. In the curing oventhe mat is heated (e.g., from about 300° F. to about 600° F.) and thebinder cured. The cured binder is a formaldehyde-free, water-resistantthermoset hinder that attaches the glass fibers of the mat together.Note that the drying and thermal curing may occur either sequentially,contemporaneously, or concurrently.

With respect to making binders that are water-insoluble when cured, itshould be appreciated that the ratio of the number of molar equivalentsof acid salt groups present on the polycarboxylic acid reactant(s) tothe number of molar equivalents of hydroxyl groups present on thecarbohydrate reactant(s) may be in the range from about 0.04:1 to about0.15:1. After curing, these formulations result in a water-resistantthermoset binder. In one variation, the number of molar equivalents ofhydroxyl groups present on the carbohydrate reactant(s) is about twentyfive-fold greater than the number of molar equivalents of acid saltgroups present on the polycarboxylic acid reactant(s). In anothervariation, the number of molar equivalents of hydroxyl groups present onthe carbohydrate reactant(s) is about ten-fold greater than the numberof molar equivalents of acid salt groups present on the polycarboxylicacid reactant(s). In yet another variation, the number of molarequivalents of hydroxyl groups present on the carbohydrate reactant(s)is about six-fold greater than the number of molar equivalents of acidsalt groups present on the polycarboxylic acid reactant(s).

In other embodiments of the invention, a binder that is already curedcan disposed on a material to be bound. As indicated above, most curedbinders will typically contain water-insoluble melanoidins. Accordingly,these binders will also be water-resistant thermoset binders.

As discussed below, various additives can be incorporated into thebinder composition. These additives give the binders of the presentinvention additional desirable characteristics. For example, the bindermay include a silicon-containing coupling agent. Many silicon-containingcoupling agents are commercially available from the Dow-CorningCorporation, Petrarch Systems, and by the General Electric Company.Illustratively, the silicon-containing coupling agent includes compoundssuch as silylethers and alkylsilyl ethers, each of which may beoptionally substituted, such as with halogen, alkoxy, amino, and thelike. In one variation, the silicon-containing compound is anamino-substituted silane, such as, gamma-aminopropyltriethoxy silane(General Electric Silicones, SILQUEST A-1101; Wilton, Conn.; USA). Inanother variation, the silicon-containing compound is anamino-substituted silane, for example, aminoethylaminopropyltrimethoxysilane (Dow Z-6020; Dow Chemical, Midland, Mich.; USA). In anothervariation, the silicon-containing compound isgamma-glycidoxypropyltrimethoxysilane (General Electric Silicones,SILQUEST A-187). In yet another variation, the silicon-containingcompound is an n-propylamine silane (Creanova (formerly Huls America)HYDROSIL 2627; Creanova; Somerset, N.J.; U.S.A.).

The silicon-containing coupling agents are typically present in thebinder in the range from about 0.1 percent to about 1 percent by weightbased upon the dissolved binder solids (i.e., about 0.1 percent to about1 percent based upon the weight of the solids added to the aqueoussolution). In one application, one or more of these silicon-containingcompounds can be added to the aqueous uncured binder. The binder is thenapplied to the material to be bound. Thereafter, the binder may be curedif desired. These silicone containing compounds enhance the ability ofthe binder to adhere to the matter the binder is disposed on, such asglass fibers. Enhancing the binder's ability to adhere to the matterimproves, for example, its ability to produce or promote cohesion in nonor loosely assembled substance(s)

A binder that includes a silicone containing coupling agent can beprepared by admixing about 10 to about 50 weight percent aqueoussolution of one or more polycarboxylic acid reactants, alreadyneutralized with an amine base or neutralized in situ, with about 10-50weight percent aqueous solution of one or more carbohydrate reactantshaving reducing sugar, and an effective amount of a silicon-containingcoupling agent. In one variation, one or more polycarboxylic acidreactants and one or more carbohydrate reactants, the latter havingreducing sugar, may be combined as solids, mixed with water, and themixture then treated with aqueous amine base (to neutralize the one ormore polycarboxylic acid reactants) and a silicon-containing couplingagent to generate an aqueous solution 10-50 weight percent in eachpolycarboxylic acid reactant and each carbohydrate reactant.

In another illustrative embodiment, a binder of the present inventionmay include one or more corrosion inhibitors. These corrosion inhibitorsprevent or inhibit the eating or wearing away of a substance, such as,metal caused by chemical decomposition brought about by an acid. When acorrosion inhibitor is included in a binder of the present invention,the binder's corrosivity is decreased as compared to the corrosivity ofthe binder without the inhibitor present. In one embodiment, thesecorrosion inhibitors can be utilized to decrease the corrosivity of theglass fiber-containing compositions described herein. Illustratively,corrosion inhibitors include one or more of the following, a dedustingoil, or a monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin(II)oxalate, and/or methylhydrogen silicone fluid emulsion.When included in a binder of the present invention, corrosion inhibitorsare typically present in the binder in the range from about 0.5 percentto about 2 percent by weight based upon the dissolved binder solids.

By following the disclosed guidelines, one of ordinary skill in the artwill be able to vary the concentrations of the reactants of the aqueousbinder to produce a wide range of binder compositions. In particular,aqueous binder compositions can be formulated to have an alkaline pH.For example, a pH in the range from greater than or equal to about 7 toless than or equal to about 10. Examples of the binder reactants thatcan be manipulated include (i) the polycarboxylic acid reactant(s), (ii)the amine base, (iii) the carbohydrate reactant(s), (iv) thesilicon-containing coupling agent, and (v) the corrosion inhibitorcompounds. Having the pH of the aqueous binders (e.g. uncured binders)of the present invention in the alkaline range inhibits the corrosion ofmaterials the binder comes in contact with, such as machines used in themanufacturing process (e.g., in manufacturing fiberglass). Note this isespecially true when the corrosivity of acidic binders is compared tobinders of the present invention. Accordingly, the “life span” of themachinery increases while the cost of maintaining these machinesdecreases. Furthermore, standard equipment can be used with the bindersof the present invention, rather than having to utilize relativelycorrosive resistant machine components that come into contact withacidic binders, such as stainless steel components. Therefore, thebinders disclosed herein decrease the cost of manufacturing boundmaterials.

The following examples illustrate specific embodiments in furtherdetail. These examples are provided for illustrative purposes only andshould not be construed as limiting the invention or the inventiveconcept to any particular physical configuration in any way. Forinstance, although 25% (weight percent) aqueous solutions each oftriammonium citrate and dextrose monohydrate were admixed in EXAMPLE 1to prepare aqueous binders, it is to be understood that, in variationsof the embodiments described herein, the weight percent of the aqueous,polycarboxylic acid ammonium salt reactant solution and the weightpercent of the aqueous, reducing-sugar carbohydrate reactant solutionmay be altered without affecting the nature of the invention described.For example, admixing aqueous solutions of the polycarboxylic acidammonium salt reactant and the reducing-sugar carbohydrate reactant theweight percents of which fall within the range from about 10-50 weightpercent. Further, although aqueous solutions 10-50% (weight percent) intriammonium citrate and dextrose monohydrate dissolved solids were usedin EXAMPLES 8-12 to prepare binder/glass fiber compositions, it is to beunderstood that the weight percent of the aqueous, polycarboxylic acidammonium salt reactant-containing/reducing-sugar carbohydratereactant-containing solution may be altered without affecting the natureof the invention described. For example, preparing aqueous solutionsincluding the polycarboxylic acid ammonium salt reactant and thereducing-sugar carbohydrate reactant the weight percents of which falloutside the range of about 10-50 weight percent. In addition, althoughthe following examples include an ammonium, i.e., NH₄, salt of apolycarboxylic acid as the polycarboxylic acid ammonium salt reactant,it is to be understood that alternative amine reactants may be usedwithout affecting the nature of the invention described, such as,including a primary amine salt or a secondary amine salt of apolycarboxylic acid.

Example 1 Preparation of Aqueous Triammonium Citrate-Dextrose Binders

Aqueous triammonium citrate-dextrose binders were prepared according tothe following procedure: Aqueous solutions (25%) of triammonium citrate(81.9 g citric acid, 203.7 g water, and 114.4 g of a 19% percentsolution of ammonia) and dextrose monohydrate (50.0 g of dextrosemonohydrate in 150.0 g water) were combined at room temperature in thefollowing proportions by volume: 1:24, 1:12, 1:8, 1:6, 1:5, 1:4, and1:3, where the relative volume of triammonium citrate is listed as “1.”For example, 10 mL of aqueous triammonium citrate mixed with 50 mL ofaqueous dextrose monohydrate afforded a “1:5” solution, wherein the massratio of triammonium citrate to dextrose monohydrate is about 1:5, themolar ratio of triammonium citrate to dextrose monohydrate is about 1:6,and the ratio of the number of molar equivalents of acid salt groups,present on triammonium citrate, to the number of molar equivalents ofhydroxyl groups, present on dextrose mono hydrate, is about 0.10:1. Theresulting solutions were stirred at room temperature for severalminutes, at which time 2-g samples were removed and thermally cured asdescribed in Example 2.

Example 2 Preparation of Cured Triammonium Citrate-Dextrose BinderSamples from Aqueous Triammonium citrate-Dextrose Binders

2-g samples of each binder, as prepared in Example 1, were placed ontoeach of three individual 1-g aluminum bake-out pans. Each binder wasthen subjected to the following three conventional bake-out/cureconditions in pre-heated, thermostated convection ovens in order toproduce the corresponding cured binder sample: 15 minutes at 400° F., 30minutes at 350° F., and 30 minutes at 300° F.

Example 3 Testing/Evaluation of Cured Triammonium Citrate-DextroseBinder Samples Produced from Aqueous Triammonium Citrate-DextroseBinders

Wet strength was determined for each cured triammonium citrate-dextrosebinder sample, as prepared in Example 2, by the extent to which a curedbinder sample appeared to remain intact and resist dissolution,following addition of water to the aluminum bake-out pan and subsequentstanding at room temperature. Wet strength was noted as Dissolved (forno wet strength), Partially Dissolved (for minimal wet strength),Softened (for intermediate wet strength), or Impervious (for high wetstrength, water-insoluble). The color of the water resulting from itscontact with cured ammonium citrate-dextrose binder samples was alsodetermined. Table 1 below shows illustrative examples of triammoniumcitrate-dextrose binders prepared according to Example 1, curingconditions therefor according to Example 2, and testing and evaluationresults according to Example 3.

Example 4 Elemental Analysis of Cured Triammonium Citrate-Dextrose (1:6)Binder Samples

Elemental analyses for carbon, hydrogen, and nitrogen (i.e., C, H, N)were conducted on 5-g samples of 15% triammonium citrate-dextrose (1:6)binder, prepared as described in Example 1 and cured as described below,which 0.75-g cured samples included a molar ratio of triammonium citrateto dextrose monohydrate of about 1:6. Binder samples were cured as afunction of temperature and time as follows: 300° F. for 1 hour; 350° F.for 0.5 hour; and 400° F. for 0.33 hour. Elemental analyses wereconducted at Galbraith Laboratories, Inc. in Knoxville, Tenn. As shownin Table 2, elemental analysis revealed an increase in the C:N ratio asa function of increasing temperature over the range from 300° F. to 350°F., which results are consistent with a melanoidin-containing binderhaving been prepared. Further, an increase in the C:H ratio as afunction of increasing temperature is also shown in Table 2, whichresults are consistent with dehydration, a process known to occur duringformation of melanoidins, occurring during binder cure.

Example 5 Preparation of Ammonium Polycarboxylate-Sugar Binders Used toConstruct Glass Bead Shell Bones, Glass Fiber-Containing Mats, and WoodFiber Board Compositions

Aqueous triammonium citrate-dextrose (1:6) binders, which binders wereused to construct glass bead shell bones and glass fiber-containingmats, were prepared by the following general procedure: Powdereddextrose monohydrate (915 g) and powdered anhydrous citric acid (152.5g) were combined in a 1-gallon reaction vessel to which 880 g ofdistilled water was added. To this mixture were added 265 g of 19%aqueous ammonia with agitation, and agitation was continued for severalminutes to achieve complete dissolution of solids. To the resultingsolution were added 3.3 g of SILQUEST A-1101 silane to produce a pH˜8-9solution (using paper), which solution contained approximately 50%dissolved dextrose monohydrate and dissolved ammonium citrate solids (asa percentage of total weight of solution); a 2-g sample of thissolution, upon thermal curing at 400° F. for 30 minutes, would yield 30%solids (the weight loss being attributed to dehydration during thermosetbinder formation). Where a silane other than SILQUEST A-1101 wasincluded in the triammonium citrate-dextrose (1:6) binder, substitutionswere made with SILQUEST A-187 Silane, HYDROSIL 2627 Silane, or Z-6020Silane. When additives were included in the triammonium citrate-dextrose(1:6) binder to produce binder variants, the standard solution wasdistributed among bottles in 300-g aliquots to which individualadditives were then supplied.

The FT-IR spectrum of a dried (uncured) triammonium citrate-dextrose(1:6) binder, which spectrum was obtained as a microscopic thin filmfrom a 10-g sample of a 30% (dissolved binder solids) binder dried invacuo, is shown in FIG. 3. The FT-IR spectrum of a cured triammoniumcitrate-dextrose (1:6) Maillard binder, which spectrum was obtained as amicroscopic thin film from a 10-g sample of a 30% binder (dissolvedbinder solids) after curing, is shown in FIG. 4.

When polycarboxylic acids other than citric acid, sugars other thandextrose, and/or additives were used to prepare aqueous ammoniumpolycarboxylate-sugar binder variants, the same general procedure wasused as that described above for preparation of an aqueous triammoniumcitrate-dextrose (1:6) binder. For ammonium polycarboxylate-sugar bindervariants, adjustments were made as necessary to accommodate theinclusion of, for example, a dicarboxylic acid or a polymericpolycarboxylic acid instead of citric acid, or to accommodate theinclusion of, for example, a triose instead of dextrose, or toaccommodate the inclusion of, for example, one or more additives. Suchadjustments included, for example, adjusting the volume of aqueousammonia necessary to generate the ammonium salt, adjusting the gramamounts of reactants necessary to achieve a desired molar ratio ofammonium polycarboxylate to sugar, and/or including an additive in adesired weight percent.

Example 6 Preparation/Weathering/Testing of Glass Bead Shell BoneCompositions Prepared with Ammonium Polycarboxylate-Sugar Binders

When evaluated for their dry and “weathered” tensile strength, glassbead-containing shell bone compositions prepared with a given binderprovide an indication of the likely tensile strength and the likelydurability, respectively, of fiberglass insulation prepared with thatparticular binder. Predicted durability is based on a shell bone'sweathered tensile strength:dry tensile strength ratio. Shell bones wereprepared, weathered, and tested as follows:

Preparation Procedure for Shell Bones:

A shell bone mold (Dietert Foundry Testing Equipment; Heated ShellCuring Accessory, Model 366, and Shell Mold Accessory) was set to adesired temperature, generally 425° F., and allowed to heat up for atleast one hour. While the shell bone mold was heating, approximately 100g of an aqueous ammonium polycarboxylate-sugar binder (generally 30% inbinder solids) was prepared as described in Example 5. Using a largeglass beaker, 727.5 g of glass beads (Quality Ballotini impact Beads,Spec. AD, US Sieve 70-140, 106-212 micron-#7, from Potters Industries,Inc.) were weighed by difference. The glass beads were poured into aclean and dry mixing bowl, which bowl was mounted onto an electric mixerstand. Approximately 75 g of aqueous ammonium polycarboxylate-sugarbinder were obtained, and the binder then poured slowly into the glassbeads in the mixing bowl. The electric mixer was then turned on and theglass beads/ammonium polycarboxylate-sugar binder mixture was agitatedfor one minute. Using a large spatula, the sides of the whisk (mixer)were scraped to remove any clumps of binder, while also scraping theedges wherein the glass beads lay in the bottom of the bowl. The mixerwas then turned back on for an additional minute, then the whisk (mixer)was removed from the unit, followed by removal of the mixing bowlcontaining the glass beads/ammonium polycarboxylate-sugar bindermixture. Using a large spatula, as much of the binder and glass beadsattached to the whisk (mixer) as possible were removed and then stirredinto the glass beads/ammonium polycarboxylate-sugar binder mixture inthe mixing bowl. The sides of the bowl were then scraped to mix in anyexcess binder that might have accumulated on the sides. At this point,the glass beads/ammonium polycarboxylate-sugar binder mixture was readyfor molding in a shell bone mold.

The slides of the shell bone mold were confirmed to be aligned withinthe bottom mold platen. Using a large spatula, a glass beads/ammoniumpolycarboxylate-sugar binder mixture was then quickly added into thethree mold cavities within the shell bone mold. The surface of themixture in each cavity was flattened out, while scraping off the excessmixture to give a uniform surface area to the shell bone. Anyinconsistencies or gaps that existed in any of the cavities were filledin with additional glass beads/ammonium polycarboxylate-sugar bindermixture and then flattened out. Once a glass heads/ammoniumpolycarboxylate-sugar binder mixture was placed into the shell bonecavities, and the mixture was exposed to heat, curing began. Asmanipulation time can affect test results, e.g., shell bones with twodifferentially cured layers can be produced, shell bones were preparedconsistently and rapidly. With the shell bone mold filled, the topplaten was quickly placed onto the bottom platen. At the same time, orquickly thereafter, measurement of curing time was initiated by means ofa stopwatch, during which curing the temperature of the bottom platenranged from about 400° F. to about 430° F., while the temperature of thetop platen ranged from about 440° F. to about 470° F. At seven minuteselapsed time, the top platen was removed and the slides pulled out sothat all three shell bones could be removed. The freshly made shellbones were then placed on a wire rack, adjacent to the shell bone moldplaten, and allowed to cool to room temperature. Thereafter, each shellbone was labeled and placed individually in a plastic storage baglabeled appropriately. If shell bones could not be tested on the daythey were prepared, the shell bone-containing plastic bags were placedin a desiccator unit.

Conditioning (Weathering) Procedure for Shell Bones:

A Blue M humidity chamber was turned on and then set to provideweathering conditions of 90° F. and 90% relative humidity (i.e., 90°F./90% rH). The water tank on the side of the humidity chamber waschecked and filled regularly, usually each time it was turned on. Thehumidity chamber was allowed to reach the specified weatheringconditions over a period of at least 4 hours, with a day-longequilibration period being typical. Shell bones to be weathered wereloaded quickly (since while the doors are open both the humidity and thetemperature decrease), one at a time through the open humidity chamberdoors, onto the upper, slotted shelf of the humidity chamber. The timethat the shell bones were placed in the humidity chamber was noted, andweathering conducted for a period of 24 hours. Thereafter, the humiditychamber doors were opened and one set of shell bones at a time werequickly removed and placed individually into respective plastic storagebags, being sealed completely. Generally, one to four sets of shellbones at a time were weathered as described above. Weathered shell boneswere immediately taken to the Instron room and tested.

Test Procedure for Breaking Shell Bones:

In the Instron room, the shell bone test method was loaded on the 5500 RInstron machine while ensuring that the proper load cell was installed(i.e., Static Load Cell 5 kN), and the machine allowed to warm up forfifteen minutes. During this period of time, shell bone testing gripswere verified as being installed on the machine. The load cell waszeroed and balanced, and then one set of shell bones was tested at atime as follows: A shell bone was removed from its plastic storage bagand then weighed. The weight (in grams) was then entered into thecomputer associated with the Instron machine. The measured thickness ofthe shell bone (in inches) was then entered, as specimen thickness,three times into the computer associated with the Instron machine. Ashell bone specimen was then placed into the grips on the Instronmachine, and testing initiated via the keypad on the Instron machine.After removing a shell bone specimen, the measured breaking point wasentered into the computer associated with the Intron machine, andtesting continued until all shell bones in a set were tested.

Test results are shown in Tables 3-6, which results are mean dry tensilestrength (psi), mean weathered tensile strength (psi), and weathered:drytensile strength ratio.

Example 7 Preparation/Weathering/Testing of Glass Fiber-Containing MatsPrepared with Ammonium Polycarboxylate-Sugar (1:6) Binders

When evaluated for their dry and “weathered” tensile strength, glassfiber-containing mats prepared with a given binder provide an indicationof the likely tensile strength and the likely durability, respectively,of fiberglass insulation prepared with that particular binder. Predicteddurability is based on a glass fiber mat's “weathered” tensile strength:dry tensile strength ratio. Glass fiber mats were prepared, weathered,and tested as follows:

Preparation Procedure for Glass Fiber-Containing Mats:

A “Deckel box,” 13 inches high×13 inches wide×14 inches deep, wasconstructed of clear acrylic sheet and attached to a hinged metal frame.Under the Deckel box, as a transition from the box to a 3-inch drainpipe, was installed a system of a perforated plate and coarse metalscreen. A woven plastic belt (called a “wire”) was clamped under theDeckel box. For mixing purposes, a 5-gallon bucket equipped with aninternal, vertical rib and a high-shear air motor mixer were used.Typically, 4 gallons of water and E-glass (i.e., high-temperature glass)fibers (11 g, 22 g, or 33 g) were mixed for two minutes. A typicalE-glass had the following weight percent composition: SiO₂, 52.5%; Na₂O,0.3%; CaO, 22.5%; MgO, 1.2%; Al₂O₃, 14.5%; FeO/Fe₂O₃, 0.2%; K₂O, 0.2%;and B₂O₃, 8.6%. The drain pipe and transition under the wire hadpreviously been filled with water such that the bottom of the Deckel boxwas wetted. The aqueous, glass fiber mixture was poured into the Deckelbox and agitated vertically with a plate containing forty nine (49)one-inch holes. The slide valve at the bottom of the drain line wasopened quickly and the glass fibers collected on the wire. Ascreen-covered frame, already in place under the wire, facilitated thetransfer of the glass fiber sample. The sample was dewatered by passingover an extractor slot with 25-40 inches of water-column suction. Onepass was used for a 11-g sample, two passes were used for a 22-g sample,and three passes were used for a 33-g sample. The sample was transferredto a second screen-covered frame and the forming wire removed. Thesample was then dried and separated from the screen. Subsequently, thesample was passed over a 3-inch diameter applicator roll rotating in abath containing an aqueous ammonium polycarboxylate-sugar binder(containing 15% dissolved binder solids, prepared as described inExample 5), wherein the glass fibers were saturated with binder. Theexcess binder was extracted by passing over the extractor slot again toproduce glass fiber-containing mats, which mats were cured at 375° F.for 30 minutes in an oven having up-flow forced convection air.

Conditioning (Weathering) Procedure for Glass Fiber Mats:

Glass fiber-containing mat samples to be conditioned were placed onTEFLON-coated course-weave belt and weighted down to prevent floating. Apair of sample mats were prepared for each ammoniumpolycarboxylate-sugar binder under evaluation. The mats were conditionedat ambient temperature and humidity in an air-conditioned, but nothumidity-controlled room for at least one day. Seven test specimens werecut from each mat using a die with the proper profile; six specimenswere cut in one direction and one specimen was cut in a perpendiculardirection, with each specimen kept separate. Each specimen was 2 incheswide and narrowed down to 1 inch wide in the mid-section, while beingapproximately 12 inches long. Three specimens from each mat were placedin a “weathering” chamber at 37-38° C. and 90% relative humidity for 24hours. The weathered specimens were removed from the chamber and storedin sealable plastic bags, each bag containing a moist paper towel, untilimmediately before testing.

Test Procedure for Breaking Glass Fiber Mats:

A tensile tester was set up with a crosshead speed of 0.5 inches perminute. The clamp jaws were 2 inches wide and had approximately 1.5-inchgrips. Three dry specimens and three weathered specimens were testedfrom each mat. The dry specimens were used for binder contentmeasurement, as determined by loss on ignition (LOI).

Test results are shown in Table 7, which results are mean % LOI, meandry tensile strength (lb force), mean weathered tensile strength (lbforce), and weathered: dry tensile strength ratio.

Example 8 Preparation of Triammonium Citrate-Dextrose (1:6) Binder/GlassFiber Compositions: Uncured Blanket and Cured Blanket

Powdered dextrose monohydrate (300 lbs) and powdered anhydrous citricacid (50 lbs) were combined in a 260-gallon tote. Soft water was thenadded to achieve a volume of 235 gallons. To this mixture were added 9.5gallons of 19% aqueous ammonia, and the resulting mixture was stirred toachieve complete dissolution of solids. To the resulting solution wereadded 0.56 lbs of SILQUEST A-1101 silane to produce a solution 15.5% indissolved dextrose monohydrate and dissolved ammonium citrate solids (asa percentage of total weight of solution); a 2-g sample of thissolution, upon thermal curing at 400° F. for 30 minutes, would yield9.3% solids (the weight loss being attributed to dehydration duringthermoset binder formation). The solution was stirred for severalminutes before being transported to a binder pump where it was used inthe manufacture of glass fiber insulation, specifically, in theformation of material referred to as “wet blanket,” or uncured blanket,and “amber blanket,” or cured blanket.

Uncured blanket and cured blanket were prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally below and in U.S. Pat. No. 5,318,990, the disclosure of whichis hereby incorporated herein by reference. Typically, a binder isapplied to glass fibers as they are being produced and formed into amat, water is volatilized from the binder, and the high-solidsbinder-coated fibrous glass mat is heated to cure the binder and therebyproduce a finished fibrous glass bat which may be used, for example, asa thermal or acoustical insulation product, a reinforcement for asubsequently produced composite, etc.

A porous mat of fibrous glass was produced by fiberizing molten glassand immediately forming a fibrous glass mat on a moving conveyor. Glasswas melted in a tank and supplied to a fiber forming device such as aspinner or a bushing. Fibers of glass were attenuated from the deviceand then blown generally downwardly within a forming chamber. The glassfibers typically have a diameter from about 2 to about 9 microns andhave a length from about 0.25 inch to about 3 inches. Typically, theglass fibers range in diameter from about 3 to about 6 microns, and havea length from about 0.5 inch to about 1.5 inches. The glass fibers weredeposited onto a perforated, endless forming conveyor. A binder wasapplied to the glass fibers, as they were being formed, by means ofsuitable spray applicators so as to result in a distribution of thebinder throughout the formed mat of fibrous glass. The glass fibers,having the uncured binder adhered thereto, were gathered and formed intoa mat on the endless conveyor within the forming chamber with the aid ofa vacuum drawn through the mat from below the forming conveyor. Theresidual heat contained in the glass fibers as well as the air flowthrough the mat caused a majority of the water to volatilize from themat before it exited the forming chamber. (Water was removed to theextent the uncured binder functioned as a binder; the amount of water tobe removed for any particular application can be determined buy one ofordinary skill in the art with routine experimentation)

As the high-solids binder-coated fibrous glass mat emerged from theforming chamber, it expanded vertically due to the resiliency of theglass fibers. The expanded mat was then conveyed to and through a curingoven wherein heated air is passed through the mat to cure the binder.Flights above and below the mat slightly compressed the mat to give thefinished product a predetermined thickness and surface finish.Typically, the curing oven was operated at a temperature over a rangefrom about 350° F. to about 600° F. Generally, the mat resided withinthe oven for a period of time from about 0.5 minute to about 3 minutes.For the manufacture of conventional thermal or acoustical insulationproducts, the time ranges from about 0.75 minute to about 1.5 minutes.The fibrous glass having a cured, rigid binder matrix emerged from theoven in the form of a bat which may be compressed for packaging andshipping and which will thereafter substantially recover its as-madevertical dimension when unconstrained. By way of example, a fibrousglass mat which is about 1.25 inches thick as it exits from the formingChamber, will expand to a vertical thickness of about 9 inches in thetransfer zone, and will be slightly compressed to a vertical thicknessof about 6 inches in the curing oven.

Nominal specifications of the cured blanket product prepared asdescribed above were about 0.09 pounds per square foot weight, about 0.7pounds per cubic foot density, about 1.5 inch thick, fiber diameter ofabout 22 hundred thousandths of an inch (5.6 microns), about 11% bindercontent after curing, and about 0.7% mineral oil content for dedusting(dedusting oil). Curing oven temperature was set at about 460° F.Uncured blanket exited the forming chamber white to off-white inapparent color, whereas cured blanket exited the oven dark brown inapparent color and well bonded. After collecting a few rolls of thecured blanket, the matt was broken before the oven, and uncured blanketwas also collected for experimentation.

Example 9 Preparation of Triammonium Citrate-Dextrose (1:6) Binder/GlassFiber Composition: Air Duct Board

Powdered dextrose monohydrate (1800 lbs) and powdered anhydrous citricacid (300 lbs) were combined in a 2000-gallon mixing tank that contained7432 gallons of soft water. To this mixture were added 52.9 gallons of19% aqueous ammonia under agitation, and agitation was continued forapproximately 30 minutes to achieve complete dissolution of solids. Tothe resulting solution were added 9 lbs of SILQUEST A-1101 silane toproduce a pH˜8 solution (using pH paper), which solution containedapproximately 25% dissolved dextrose monohydrate and dissolved ammoniumcitrate solids (as a percentage of total weight of solution); a 2-gsample of this solution, upon thermal curing at 400° F. for 30 minutes,would yield 15% solids (the weight loss being attributed to dehydrationduring thermoset binder formation). The solution was stirred for severalminutes before being transferred to a binder hold tank from which it wasused in the manufacture of glass fiber insulation, specifically, in theformation of a product called “air duct board.”

Air duct board was prepared using conventional fiberglass manufacturingprocedures; such procedures are described generally in Example 8.Nominal specifications of the air duct board product were about 0.4pounds per square foot density, about 4.5 pounds per cubic foot density,at 1 inch thick, with a fiber diameter of about 32 hundred thousandthsof an inch (8.1 microns), and a binder content of about 14.3%, with 0.7%mineral oil for dedusting (dedusting oil). Curing oven temperature wasset at about 550° F. Product exited the oven dark brown in apparentcolor and well bonded.

Example 10 Preparation of Triammonium citrate-Dextrose (1:6)Binder/Glass Fiber Composition: R30 Residential Blanket

Powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citricacid (200 lbs) were combined in a 2000-gallon mixing tank that contained1104 gallons of soft water. To this mixture were added 42.3 gallons of19% aqueous ammonia under agitation, and agitation was continued forapproximately 30 minutes to achieve complete dissolution of solids. Tothe resulting solution were added 6 lbs of SILQUEST A-1101 silane toproduce a pH˜8 solution (using pH paper), which solution containedapproximately 13.4% dissolved dextrose monohydrate and dissolvedammonium citrate solids (as a percentage of total weight of solution); a2-g sample of this solution, upon thermal curing at 400° F. for 30minutes, would yield 8% solids (the weight loss being attributed todehydration during thermoset binder formation). The solution was stirredfor several minutes before being transferred to a binder hold tank fromwhich it was used in the manufacture of glass fiber insulation,specifically, in the formation of a product called “R30 residentialblanket.”

R30 residential blanket was prepared using conventional fiberglassmanufacturing procedures; such procedures are described generally inExample 8. Nominal specifications of the R30 residential blanket productwere about 0.4 pound per square foot weight, a target recovery of 10inches thick at the end of the line, with a fiber diameter of 18 hundredthousandths of an inch (4.6 microns), 3.8% binder content, and 0.7%mineral oil content for dedusting (dedusting oil). Curing oventemperature was set at about 570° F. Product exited the oven brown inapparent color and well bonded.

Example 11 Preparation of Triammonium citrate-Dextrose (1:6)Binder/Glass Fiber Composition: R19 Residential Blanket

Batch A-1:

Powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citricacid (200 lbs) were combined in a 2000 gallon mixing tank that contained1104 gallons of soft water. To this mixture were added 35.3 gallons of19% ammonia under agitation, and agitation was continued forapproximately 30 minutes to achieve complete dissolution of solids. Tothe resulting solution were added 6 lbs of SILQUEST A-1101 silane toproduce a pH˜8 solution (using pH paper), which solution contained about13.3% dissolved dextrose monohydrate and ammonium citrate solids (as apercentage of total weight of solution); a 2-g sample of this solution,upon thermal curing at 400° F. for 30 minutes, would yield 8% solids(the weight loss being attributed to dehydration during thermoset binderformation). The solution was stirred for several minutes before beingtransferred to a binder hold tank from which it was used in themanufacture of glass fiber insulation, specifically, in the formation ofa product called “R19 Residential Blanket.”

R19 Residential Blanket, Batch A-1, was prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally in Example 8. Nominal specifications of the R19 ResidentialBlanket product were about 0.2 pound per square foot weight, 0.2 poundper cubic foot density, a target recovery of 6.5 inches thick at the endof the line, with a fiber diameter of 18 hundred thousandths of an inch(4.6 microns), 3.8% binder content, and 0.7% mineral oil content (fordedusting). Curing oven temperature was set at about 570° F. Productexited the oven brown in apparent color and well bonded.

Batch A-2:

Powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citricacid (200 lbs) were combined in a 2000 gallon mixing tank that contained558 gallons of soft water. To this mixture were added 35.3 gallons of19% ammonia under agitation, and agitation was continued forapproximately 30 minutes to achieve complete dissolution of solids. Tothe resulting solution were added 5 lbs of SILQUEST A-1101 silane toproduce a pH˜8 solution (using pH paper), which solution contained about20.5% dissolved dextrose monohydrate and ammonium citrate solids (as apercentage of total weight of solution); a 2-g sample of this solution,upon thermal curing at 400° F. for 30 minutes, would yield 12% solids(the weight loss being attributed to dehydration during thermoset binderformation). The solution was stirred for several minutes before beingtransferred to a binder hold tank from which it was used in themanufacture of glass fiber insulation, specifically, in the formation ofa product called “R19 Residential Blanket.”

R19 Residential Blanket, Batch A-2, was prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally in Example 8. Nominal specifications of the R19 ResidentialBlanket product were about 0.2 pound per square foot weight, about 0.4pound per cubic foot density, a target recovery of 6.5 inches thick atthe end of the line, with a fiber diameter of 18 hundred thousandths ofan inch (4.6 microns), 3.8% binder content, and 0.7% mineral oil content(for dedusting). Curing oven temperature was set at about 570° F.Product exited the oven brown in apparent color and well bonded.

Batch B:

Powdered dextrose monohydrate (300 lbs) and powdered anhydrous citricacid (50 lbs) were combined in a 260 gallon International Bulk Container(IBC) that already contained 167 gallons of distilled water. To thismixture were added 10.6 gallons of 19% ammonia under agitation, andagitation was continued for approximately 30 minutes to achieve completedissolution of solids. To the resulting solution were added 1.5 lbs ofSILQUEST A-1101 silane to produce a pH˜8 solution (using pH paper),which solution contained approximately 20.1% dissolved dextrosemonohydrate and ammonium citrate solids (as a percentage of total weightof solution); a 2-g sample of this solution, upon thermal curing at 400°F. for 30 minutes, would yield 12% solids (the weight loss beingattributed to dehydration during thermoset binder formation). The IBCcontaining the aqueous binder was transferred to an area at whichlocation the binder was pumped into the binder spray rings in theforming hood, diluted thereinto with distilled water, and then used inthe manufacture of glass fiber insulation, specifically, in theformation of a product called “R19 Residential Blanket.”

R19 Residential Blanket, Batch B, was prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally in Example 8. Nominal specifications of the R19 ResidentialBlanket product made were about 0.2 pound per square foot weight, andabout 0.4 pound per cubic foot density, a target recovery of 6.5 inchesthick at the end of the line, with a fiber diameter of 18 hundredthousandths of an inch (4.6 microns), 3.8% binder content, and 0.7%mineral oil content (for dedusting). Curing oven temperature was set atabout 570° F. Product exited the oven brown in apparent color and wellbonded.

Batch C:

Powdered dextrose monohydrate (300 lbs) and powdered anhydrous citricacid (50 lbs) were combined in a 260 gallon international Bulk Container(IBC) that already contained 167 gallons of distilled water. To thismixture were added 10.6 gallons of 19% ammonia under agitation, andagitation was continued for about 30 minutes to achieve completedissolution of solids. To the resulting solution were added 1.5 lbs ofSILQUEST A-1101 silane followed by 1.80 gallons of the methylhydrogenemulsion BS 1040 (manufactured by the Wacker Chemical Corporation) toproduce a pH˜8 solution (using pH paper), which solution containedapproximately 20.2% dissolved dextrose monohydrate and ammonium citratesolids (as a percentage of total weight of solution); a 2-g sample ofthis solution, upon thermal curing at 400° F. for 30 minutes, wouldyield 12% solids (the weight loss being attributed to dehydration duringthermoset binder formation). The IBC containing the aqueous binder wastransferred to an area at which location the binder was pumped into thebinder spray rings in the forming hood, diluted thereinto with distilledwater, and then used in the manufacture of glass fiber insulation,specifically, in the formation of a product called “R19 ResidentialBlanket.”

R19 Residential Blanket, Batch C, was prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally in Example 8. Nominal specifications of the R19 ResidentialBlanket product made was about 0.2 pound per square foot density, about0.4 pound per cubic foot weight, a target recovery of 6.5 inches thickat the end of the line, with a fiber diameter of 18 hundred thousandthsof an inch (4.6 microns), 3.8% binder content, and 0.7% mineral oilcontent (for dedusting). Curing oven temperature was set at about 570 T.Product exited the oven brown in apparent color and well bonded.

Batch D:

Powdered dextrose monohydrate (300 lbs) and powdered anhydrous citricacid (50 lbs) were combined in a 260 gallon International Bulk Container(IBC) that already contained 167 gallons of distilled water. To thismixture were added 10.6 gallons of 19% ammonia under agitation, andagitation was continued for approximately 30 minutes to achieve completedissolution of solids. To the resulting solution were added 1.5 lbs ofSILQUEST A-1101 silane followed by 22 lbs of the clay product BentaliteL10 (manufactured by Southern Clay Products) to produce a pH˜8 solution(using pH paper), which solution contained about 21.0% dissolveddextrose monohydrate and ammonium citrate solids (as a percentage oftotal weight of solution); a 2-g sample of this solution, upon thermalcuring at 400° F. for 30 minutes, would yield 12.6% solids (the weightloss being attributed to dehydration during thermoset binder formation).The IBC containing the aqueous Maillard binder was transferred to anarea at Which location the binder was pumped into the binder spray ringsin the forming hood, diluted thereinto with distilled water, and thenused in the manufacture of glass fiber insulation, specifically, in theformation of a product called “R19 Residential Blanket.”

R19 Residential Blanket, Batch D, was prepared using conventionalfiberglass manufacturing procedures; such procedures are describedgenerally in Example 8. Nominal specifications of the R19 ResidentialBlanket product made that day were about 0.2 pound per square footweight, about 0.4 pound per cubic foot density, a target recovery of 6.5inches thick at the end of the line, with a fiber diameter of 18 hundredthousandths of an inch (4.6 microns), 3.8% binder content, and 0.7%mineral oil content (for dedusting). Curing oven temperature was set atabout 570° F. Product exited the oven brown in apparent color and wellbonded.

Example 12 Preparation of Triammonium citrate-Dextrose (1:6)Binder/Glass Fiber Composition: Pipe Insulation Uncured

Powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citricacid (200 lbs) were combined in a 2000-gallon mixing tank that contained215 gallons of soft water. To this mixture were added 42.3 gallons of19% aqueous ammonia under agitation, and agitation was continued forapproximately 30 minutes to achieve complete dissolution of solids. Tothe resulting solution were added 6 lbs of SILQUEST A-1101 silane toproduce a pH˜8 solution (using pH paper), which solution containedapproximately 41.7% dissolved dextrose monohydrate and dissolvedammonium citrate solids (as a percentage of total weight of solution); a2-g sample of this solution, upon thermal curing at 400° F. for 30minutes, would yield 25% solids (the weight loss being attributed todehydration during thermoset binder formation). The solution was stirredfor several minutes before being transferred to a binder hold tank fromwhich it was used in the manufacture of glass fiber insulation,specifically, in the formation of a product called “pipe insulationuncured.”

Pipe insulation uncured was prepared using conventional fiberglassmanufacturing procedures; such procedures are described generally inExample 8. Nominal specifications of the pipe insulation uncured productwere about 0.07 pound per square foot weight, about 0.85 pound per cubicfoot density, an estimated thickness of 1 inch, a fiber diameter of 30hundred thousandths of an inch (7.6 microns), and a binder content of 7%when cured. Pipe insulation uncured was transported to a pipeinsulation-forming area, where it was cast into cylindrical shells, with6-inch walls and a 3-inch diameter hole and 4-pound per cubic footdensity, to be used as pipe insulation. These shells were cured with thecuring oven set at approximately 450° F. to produce dark brown,well-bonded pipe insulation product. Shells cured at higher temperaturesexhibited punking and could not be used further for testing.

Example 13 Preparation of Triammonium citrate-Dextrose (1:6)Binder/Cellulose Fiber Composition: Wood Fiber Board

Several methods were used to produce wood fiber boards/sheets bondedwith triammonium citrate-dextrose (1:6) binder. A representative method,which method produced strong, uniform samples, is as follows: Wood inthe form of assorted pine wood shavings and sawdust was purchased from alocal farm supply store. Wood fiber board samples were made with the “asreceived” wood and also material segregated into the shavings andsawdust components. Wood was first dried in an oven at approximately200° F. over night, which drying resulted in moisture removal of 14-15%for the wood shavings and about 11% for the sawdust. Thereafter, driedwood was placed in an 8 inch high×12 inch wide×10.5 inch deep plasticcontainer (approximate dimensions). Triammonium citrate-dextrose (1:6)binder was prepared (36% in binder solids) as described in Example 5,and then 160 g of binder was sprayed via an hydraulic nozzle onto a400-g sample of wood in the plastic container while the container wasinclined 30-40 degrees from the vertical and rotated slowly(approximately 5-15 rpm). During this treatment, the wood was gentlytumbled while becoming uniformly coated.

Samples of resinated wood were placed in a collapsible frame andcompressed in between heated platens under the following conditions:resinated wood shavings, 300 psi; resinated sawdust, 600 psi. For eachresinated sample, the cure conditions were 350° F. for 25 to 30 minutes.The resulting sample boards were approximately 10 inches long×10 incheswide, and about 0.4 inches thick before trimming, well-bondedinternally, smooth surfaced and made a clean cut when trimmed on theband saw. Trimmed sample density and the size of each trimmed sampleboard produced were as follows: sample board from wood shavings, density˜54 pcf, size ˜8.3 inches long×9 inches wide×0.36 inches thick; sampleboard from sawdust, density 44 pcf, size˜8.7 inches long×8.8 incheswide×0.41 inches thick. The estimated binder content of each sampleboard was ˜12.6%.

Example 14 Testing/Evaluation of Triammonium Citrate-Dextrose (1:6)Binder/Glass Fiber Compositions

The triammonium citrate-dextrose (1:6) binder/glass fiber compositionsfrom Examples 8-12, i.e., cured blanket, air duct board, R30 residentialblanket, R19 residential blanket, and pipe insulation uncured, weretested versus a corresponding phenol-formaldehyde (PF) binder/glassfiber composition for one or more of the following: product emissions,density, loss on ignition, thickness recovery, dust, tensile strength,parting strength, durability of parting strength, bond strength, waterabsorption, hot surface performance, corrosivity on steel, flexuralrigidity, stiffness-rigidity, compressive resistance, conditionedcompressive resistance, compressive modulus, conditioned compressivemodulus, and smoke development on ignition. The results of these testsare shown in Tables 8-13. Also determined were the gaseous compoundsproduced during pyrolysis of cured blanket from Example 8, and thegaseous compounds produced during thermal curing of pipe insulationuncured from Example 12; these testing results are shown in Tables14-15. Hot surface performance for cured pipe insulation is shown inFIG. 5 and FIG. 6. Specific tests conducted and conditions forperforming these tests are as follows:

Product Emissions Testing

Product emissions for cured blanket from Example 8 and air duct boardfrom Example 9 were determined in accordance with AQS Greenguard Testingprocedures. The insulation products were monitored for emissions oftotal volatile organic compounds (TVOCs), formaldehyde, total selectedaldehydes in accordance with ASTM D5116 (“Standard Guide for Small-ScaleEnvironmental Chamber Determinations of Organic Emissions from IndoorMaterials/Products”), the United States Environmental Protection Agency(USEPA), and the State of Washington IAQ Specification of January, 1994.The emission data were collected over a one-week exposure period and theresultant air concentrations were determined for each of theaforementioned substances. Air concentration predictions were computermonitored based on the State of Washington requirements, which include astandard room loading and ASHRAE Standard 62-1999 ventilationconditions. Product loading is based on standard wall usage of 28.1 m²in a 32 m³ room.

Emissions Testing—Selected Aldehydes

The insulation products were tested in a small-sized environmentalchamber 0.0855 m³ in volume with the chemical emissions analyticallymeasured. Emission of selected aldehydes, including formaldehyde, weremeasured following ASTM D5197 (“Standard Test Method for Determinationof Formaldehyde and Other Carbonyl Compounds in Air (Active SamplerMethodology)) using high performance liquid chromatography (HPLC). Solidsorbent cartridges with 2,4-dinitrophenylhydrazine (DNPH) were used tocollect formaldehyde and other low-molecular weight carbonyl compoundsin the chamber air. The DNPH reagent in the cartridge reacted withcollected carbonyl compounds to form the stable hydrazone derivativesretained by the cartridge. The hydrazone derivatives were eluted from acartridge with HPLC-grade acetonitrile. An aliquot of the sample wasanalyzed for low-molecular weight aldehyde hydrazone derivatives usingreverse-phase high-performance liquid chromatography (HPLC) with UVdetection. The absorbances of the derivatives were measured at 360 nm.The mass responses of the resulting peaks were determined usingmulti-point calibration curves prepared from standard solutions of thehydrazone derivatives. Measurements are reported to a quantifiable levelof 0.2 ug based on a standard air volume collection of 45 L.

Emissions Testing—Volatile Organic Compounds (VOC)

VOC measurements were made using gas chromatography with massspectrometric detection (GC/MS). Chamber air was collected onto a solidsorbent which was then thermally desorbed into the GC/MS. The sorbentcollection technique, separation, and detection analysis methodology hasbeen adapted from techniques presented by the USEPA and otherresearchers. The technique follows USEPA Method 1P-1B and is generallyapplicable to C₅-C₁₆ organic chemicals with a boiling point ranging from35° C. to 250° C. Measurements are reported to a quantifiable level of0.4 ug based on a standard air volume collection of 18 L. IndividualVOCs were separated and detected by GC/MS. The total VOC measurementswere made by adding all individual VOC responses obtained by the massspectrometer and calibrating the total mass relative to toluene.

Emissions Testing—Air Concentration Determinations

Emission rates of formaldehyde, total aldehydes, and TVOC were used in acomputer exposure model to determine the potential air concentrations ofthe substances. The computer model used the measured emission ratechanges over the one-week time period to determine the change in airconcentrations that would accordingly occur. The model measurements weremade with the following assumptions; air with open office areas in thebuilding is well-mixed at the breathing level zone of the occupiedspace; environmental conditions are maintained at 50% relative humidityand 73° F. (23° C.); there are no additional sources of thesesubstances; and there are no sinks or potential re-emitting sourceswithin the space for these substances. The USEPA's Indoor Air ExposureModel, Version 2.0, was specifically modified to accommodate thisproduct and chemicals of interest. Ventilation and occupancy parameterswere provided in ASHRAE Standard 62-1999.

Density

The density of cured blanket from Example 8 was determined in accordancewith internal test method PTL-1, “Test Method for Density and Thicknessof Blanket or Batt Thermal Insulation,” which test method is virtuallyidentical to ASTM C 167. The density of air duct board from Example 9was determined in accordance with internal test method PTL-3, “TestProcedure for Density Preformed Block-Type Thermal Insulation,” whichtest method is virtually identical to ASTM C 303.

Loss on Ignition (LOI)

The loss on ignition for cured blanket from Example 8 and air duct boardfrom Example 9 was determined in accordance with internal test methodK-157, “Ignition Loss of Cured Blanket (LOI).” The test was performed ona sample in a wire tray placed in a furnace at 1000° F., +/−50° F., for15 to 20 minutes to ensure complete oxidation, after which treatment theresulting sample was weighed.

Parting Strength

The parting strength of cured blanket from Example 8, R30 residentialblanket from Example 10, and R19 residential blanket from Example 11were determined in accordance with internal test method KRD-161, whichtest method is virtually identical to ASTM C 686, “Parting Strength ofMineral Fiber Batt and Blanket-Type Insulation.”

Durability of Parting Strength

The durability of parting strength for R30 residential blanket fromExample 10 and R19 residential blanket from Example 11 were determinedin accordance with ASTM C 686, “Parting Strength of Mineral Fiber Battand Blanket-Type Insulation,” following one-week conditioning at 90° F.and 95% relative humidity.

Tensile Strength

The tensile strength of cured blanket from Example 8 and R19 residentialblanket from Example 11 was determined in accordance with an internaltest method KRD-161, “Tensile Strength Test Procedure.” The test wasperformed on samples die cut in both the machine direction and thecross-cut machine direction. Samples were conditioned for 24 hours at75° F. and 50% relative humidity. Ten samples in each machine directionwere tested in a test environment of 75° F., 50% relative humidity. Thedogbone specimen was as specified in ASTM D638, “Standard Test Methodfor Tensile Properties of Plastics.” A cross-head speed of 2inches/minute was used for all tests.

Bond Strength

The inter-laminar bond strength of cured blanket from Example 8, R30residential blanket from Example 10, and R19 residential blanket fromExample 11 was determined using an internal test method KRD-159, “BondStrength of Fiberglass Board and Blanket Products.” Molded specimenswith a cross sectional area of 6 inches by 6 inches were glued to 6 inchby 7 inch specimen mounting plates and placed in a fixture that appliedthe force perpendicular to the surface of the specimen. A cross-headspeed of 12 inches per minute was used for all tests.

Thickness Recovery

Out-of-package and rollover thickness tests were performed on curedblanket from Example 8 using internal test methods K-123, “RecoveredThickness—End of Line Dead Pin Method—Roll Products,” and K-109, “TestProcedure for Recovered Thickness of Roll Products—Rollover Method.”Recovered thickness was measured by forcing a pin gauge through a sampleof cured blanket from a roll product, either 15 minutes after packagingor at a later point in time, until the pin contacts a flat, hard surfaceunderlying the sample, and then measuring the recovered thickness with asteel rule. Thickness tests were performed on R30 residential blanketfrom Example 10 and R19 residential blanket from Example 11 usinginternal test methods K-120, “Test Procedure for Determining End-of-LineDead-Pin Thickness—Batts,” and K-128, “Test Procedure for RecoveredThickness of Batt Products—Drop Method,” both of which test methods aresimilar to ASTM C 167, “Standard Test Methods for Thickness and Densityof Blanket or Batt Thermal Insulations.”

Dust Testing

Dust testing was performed on cured blanket from Example 8, R30residential blanket from Example 10, and R19 residential blanket fromExample 11 using internal test procedure K-102, “Packaged Fiber GlassDust Test, Batt Method.” Dust liberated from randomly selected samples(batts) of cured blanket, R30 residential blanket, and R19 residentialblanket dropped into a dust collection box was collected on a filter andthe amount of dust determined by difference weighing.

Water Absorption

Water absorption (% by weight) tests were performed on cured blanketfrom Example 8 and R19 residential blanket from Example 11 using ASTM C1104, “Test Method for Determining the Water Vapor Absorption of UnfacedMineral Fiber Insulation.”

Flexural Rigidity (EI)

The flexural rigidity of air duct board from Example 9, which is theforce couple required to bend the rigid air duct board, i.e., theproduct of E, the modulus of elasticity, and L the bending moment ofinertia, was determined in accordance with NAIMA AHS 100-74, “TestMethod for Flexural Rigidity of Rectangular Rigid Duct Materials.”

Stiffness-Rigidity

Stiffness-rigidity testing was performed on R19 residential blanket fromExample 11 using internal test procedure K-117, “Test Procedure forRigidity of Building Insulation.” A sample of R19 residential blanket,approximately 47.5 inches in length (±0.5 inch), was placed on thecenter support bar of a stiffness test apparatus, which apparatusincluded a protractor scale directly behind the center support bar. Withthe ends of the sample hanging free, the angle (in degrees) at each endof the sample was recorded by sighting along the bottom edge of thesample while reading the protractor scale.

Compressive Resistance

The compressive resistance of air duct board from Example 9 wasdetermined in accordance with ASTM C 165, “Standard Test Method forMeasuring Compressive Properties of Thermal Insulations.”

Conditioned Compressive Resistance

The conditioned compressive resistance of air duct board from Example 9,after one week at 90° F. and 95% relative humidity, was determined inaccordance with ASTM C 165, “Standard Test Method for MeasuringCompressive Properties of Thermal Insulations.”

Compressive Modulus

The compressive modulus of air duct board from Example 9 was determinedin accordance with ASTM C 165, “Standard Test Method for MeasuringCompressive Properties of Thermal insulations.”

Conditioned Compressive Modulus

The conditioned compressive modulus of air duct board from Example 9,after one week at 90° F. and 95% relative humidity, was determined inaccordance with ASTM C 165, “Standard Test Method for MeasuringCompressive Properties of Thermal Insulations.”

Hot Surface Performance

Hot surface performance tests were performed on cured blanket fromExample 8, R30 residential blanket from Example 10, and R19 residentialblanket from Example 11 using ASTM C 411, “Test Method for Hot SurfacePerformance of High Temperature Thermal Insulation.” Hot surfaceperformance tests were conducted on 3×6-inch sections of cured pipeinsulation product from Example 12 at 650° F. and 1000° F. using ASTM C411, “Test Method for Hot Surface Performance of High TemperatureThermal Insulation.” There was no measurable internal temperature risein the insulation above the pipe hot surface temperature.

Corrosivity on Steel

Corrosivity testing was performed on R30 residential blanket fromExample 10 and R19 residential blanket from Example 11 versus steelcoupons using internal test procedure Knauf PTL-14, which is virtuallyidentical to ASTM C 665.

Smoke Development on Ignition

Smoke development on ignition for cured blanket from Example 8, withcalculation of specific extinction area (SEA), was determined by conecalorimetry using ASTM E 1354, “Test Method for Heat and Visible SmokeRelease Rates for Materials and Products Using an Oxygen Consumptioncalorimeter.”

Gaseous Compounds Produced During Pyrolysis

Gaseous compounds producing during pyrolysis of cured blanket fromExample 8 were determined as follows: Approximately 10 g of curedblanket was placed in a test tube, which tube was then heated to 1000°F. for 2.5 minutes at which time the headspace was sampled and analyzedby gas chromatography/mass spectrometry (GC/MS) under the followingconditions: Oven, 50° C. for one minute—10° C./minute to 300° C. for 10minutes; Inlet, 280° C. splitless; Column, HP-5 30 mm×0.32 mm×0.25 um;Column flow, 1.11 mL/minute Helium; Detector, MSD 280° C.; Injectionvolume, 1 mL; Detector mode, scan 34-700 amu; Threshold, 50; andSampling Rate, 22 scans/second. A computer search of the mass spectrumof a chromatographic peak in the sample was made against the Wileylibrary of mass spectra. The best match was reported. A quality index(closeness of match to the library spectra) ranging from 0 to 99 wasgenerated. Only the identity of peaks with a quality index of greaterthan or equal to 90 were reported.

Gaseous Compounds Produced During Thermal Curing

Gaseous compounds producing during thermal curing of pipe insulationuncured from Example 12 were determined as follows: Approximately 0.6 gof pipe insulation uncured was placed in a test tube, which tube wasthen heated to 540° F. for 2.5 minutes at which time the headspace wassampled and analyzed by gas chromatography/mass spectrometry under thefollowing conditions: Oven, 50° C. for one minute—10° C./minute to 300°C. for 10 minutes; Inlet; 280° C. splitless; Column, HP-5 30 mm×0.32mm×0.25 urn; Column flow; 1.11 ml/minute Helium; Detector, MSD 280° C.;Injection volume, 1 mL; Detector mode, scan 34-700 amu; Threshold, 50;and Sampling Rate, 22 scans/second. A computer search of the massspectrum of a chromatographic peak in the sample was made against theWiley library of mass spectra. The best match was reported. A qualityindex (closeness of match to the library spectra) ranging from 0 to 99was generated. Only the identity of peaks with a quality index ofgreater than or equal to 90 were reported.

TABLE 1 Testing/Evaluation Results for Cured Triammoniumcitrate-Dextrose Binder Samples^(a) BINDER COMPOSITION Wet Water WetWater Wet Water Triammonium citrate ^(b):Dextrose•H₂O ^(c) StrengthColor Strength Color Strength Color Mass Ratio Mole Ratio^(d) COOH:OHRatio^(d) (400° F.) (400° F.) (350° F.) (350° F.) (300° F.) (300° F.)1:24 (1:30) 0.02:1 Dissolved Light Dissolved Light Dissolved Lightcaramel- caramel- caramel- colored colored colored 1:12 (1:15) 0.04:1Impervious Clear and Dissolved Caramel- Dissolved Caramel- colorlesscolored colored 1:8 (1:10) 0.06:1 Impervious Clear and PartiallyCaramel- Dissolved Caramel- colorless Dissolved colored colored 1:6(1:7) 0.08:1 Impervious Clear and Softened Clear Dissolved Caramel-colorless yellow colored 1:5 (1:6) 0.10:1 Impervious Clear and SoftenedClear Dissolved Caramel- colorless yellow colored 1:4^(e) (1:5)^(e)0.12:1^(e) Impervious Clear and Softened Clear Dissolved Caramel-colorless yellow colored 1:3^(e) (1:4)^(e) 0.15:1^(e) Impervious Clearand Softened Clear Dissolved Caramel- colorless orange colored ^(a)FromExample 1 ^(b) MW = 243 g/mol; 25% (weight percent) solution ^(c) MW =198 g/mol; 25% (weight percent) solution ^(d)Approximate ^(e)Associatedwith distinct ammonia smell

TABLE 2 Elemental Analysis Results for Cured Triammonium Citrate-Dextrose (1:6) Binder Samples^(a) as a Function of Temperature and TimeElemental Elemental Analysis Results Cure Temp Cure Time Analysis C:HC:N 300° F.   1 hour Carbon 48.75% 8.70 11.89 Hydrogen  5.60% Nitrogen 4.10% 300° F.   1 hour Carbon 49.47% 8.91 12.00 Hydrogen  5.55%Nitrogen  4.12% 300° F. 1 hour Carbon 50.35% 9.31 12.04 Hydrogen  5.41%Avg: 8.97 11.98 Nitrogen  4.18% 350° F.  0.5 hour Carbon 52.55% 10.1012.36 Hydrogen  5.20% Nitrogen  4.25% 350° F.  0.5 hour Carbon 54.19%10.67 12.31 Hydrogen  5.08% Nitrogen  4.40% 350° F.  0.5 hour Carbon52.86% 10.22 12.47 Hydrogen  5.17% Avg. 10.33 12.38 Nitrogen  4.24% 400°F. 0.33 hour Carbon 54.35% 10.68 12.21 Hydrogen  5.09% Nitrogen  4.45%400° F. 0.33 hour Carbon 55.63% 10.99 12.15 Hydrogen  5.06% Nitrogen 4.58% 400° F. 0.33 hour Carbon 56.10% 11.47 12.06 Hydrogen  4.89% Avg.11.05 12.14 Nitrogen  4.65% ^(a)From Example 4

TABLE 3 Measured Tensile Strength for Glass Bead Shell BoneCompositions^(a) Prepared With Triammonium Citrate-Dextrose (1:6)Binder^(b) vs. Standard PF Binder Mean^(c) Mean^(c) Dry WeatheredWeathered:Dry Tensile Tensile Tensile Strength Strength Strength BinderDescription Ratio (psi) (psi) Triammonium Citrate-Dextrose^(d) 0.71 286202 Triammonium Citrate-Dextrose^(d) 0.76 368 281 TriammoniumCitrate-Dextrose^(d) 0.79 345 271 Triammonium Citrate-Dextrose^(d) 0.77333 256 Triammonium Citrate-Dextrose^(d) 0.82 345 284 TriammoniumCitrate-Dextrose^(d) 0.75 379 286 Triammonium Citrate-Dextrose^(d) 0.74447 330 Triammonium Citrate-Dextrose^(e) 0.76^(e) 358^(e) 273^(e)Triammonium Citrate-Dextrose: Day Binder Made 0.79 345 271 1 Day AfterBinder Made 0.76 352 266 2 Day After Binder Made 0.72 379 272 1 WeekAfter Binder Made 0.88 361 316 2 Weeks After Binder Made 0.82 342 280Triammonium citrate-Dextrose with Silane Substitution: SILQUEST A-187silane 0.69 324 222 substituted 1:1 by weight for SILQUEST A-1101SILQUEST A-187 silane 0.71 351 250 substituted 2:1 by weight forSILQUEST A-1101 HYDROSIL 2627 silane 0.87 337 293 substituted 1:1 byweight for SILQUEST A-1101 HYDROSIL 2627 silane 0.99 316 312 substituted2:1 by weight for SILQUEST A-1101 Z-6020 silane substituted 1:1 by 0.78357 279 weight for SILQUEST A-1101 Z-6020 silane substituted 2:1 by 0.78373 291 weight for SILQUEST A-1101 Standard PF (Ductliner) Binder 0.79637 505 ^(a)From Example 6 ^(b)From Example 5 ^(c)Mean of nine shellbone samples ^(d)One of seven different batches of triammoniumcitrate-dextrose (1:6) binder made over a five-month period ^(e)Averageof seven different batches of triammonium citrate-dextrose (1:6) bindermade over a five-month period

TABLE 4 Measured Tensile Strength for Glass Bead Shell BoneCompositions^(a) Prepared With Triammonium Citrate-Dextrose (1:6) BinderVariants^(b) vs. Standard PF Binder Quantity of Mean^(c) Mean^(c)Additive in Weathered:Dry Dry Weathered 300 g of Tensile Tensile Tensilebinder Strength Strength Strength Binder Description (grams) Ratio (psi)(psi) Triammonium citrate-Dextrose^(d) — 0.76^(d) 358^(d) 273^(d)Triammonium citrate-Dextrose with Additive: Silres BS 1042^(e) 1.6 0.84381 325 Silres BS 1042 3.2 0.94 388 363 Silres BS 1042 4.8 1.01 358 362Sodium Carbonate 0.45 0.88 281 248 Sodium Carbonate 0.9 0.71 339 242Sodium Carbonate 1.35 0.89 282 251 Silres BS 1042 + Sodium Carbonate1.6 + 1.35 0.84 335 280 Silres BS 1042 + Sodium Carbonate 3.2 + 0.9 0.93 299 277 Silres BS 1042 + Sodium Carbonate 4.8 + 0.48 0.73 368 270Sodium Carbonate^(f) 0.9 0.83 211 175 Sodium Carbonate^(f) 0.9 0.69 387266 Sodium Carbonate 1.8 0.81 222 180 Sodium Carbonate^(g) 1.8 0.66 394259 LE 46^(h) 6.4 0.80 309 248 LE 46 12.9 0.98 261 256TPX5688/AQUA-TRETE BSM40^(i) 5.6 0.78 320 250 Silres BS 1042 6.4 0.91308 280 Trimethylmethoxysilane 0.9 0.78 262 205 Potassium Permanganate0.2 0.69 302 207 PGN^(j) 9 0.82 246 201 Cloisite NA+^(k) 9 0.71 280 199Blown Soya Emulsion (25%)^(l) 18 1.04 239 248 Flaxseed Oil Emulsion(25%) 18 0.90 362 326 Bentolite L-10^(m) 9 1.00 288 288 Michem 45745 PEEmulsion (50%)^(n) 9 0.81 335 270 Bone Glue Solution^(o) 15 0.82 435 358Tannic Acid 4.5 0.79 474 375 Glycine 4.5 0.80 346 277 Glycerol 5.28 0.69361 249 Sodium Tetraborate Decahydrate + 0.9 + 4.5  0.74 378 280Glycerol Sodium Tetraborate Decahydrate 1% 0.9 0.86 387 331 SodiumTetraborate Decahydrate 2% 1.8 0.80 335 267 Sodium TetraborateDecahydrate 3% 2.5 0.84 334 282 Axel INT-26-LF95^(p) 0.9 0.70 374 263ISO Chill Whey^(q) 1% 0.9 0.74 444 328 ISO Chill Whey 2% 1.8 1.01 407412 ISO Chill Whey 5% 4.5 NC^(r) 473 NM^(s) Resorcinol 5% 4.5 0.76 331251 Maltitol 3.23 0.82 311 256 Standard PF (Ductliner) Binder — 0.79 637505 ^(a)From Example 6 ^(b)From Example 5 ^(c)Mean of nine shell bonesamples ^(d)Average of seven different batches of triammoniumcitrate-dextrose (1:6) binder made over a five-month period ^(e)SilresBS 1042 to be 50% solids emulsion of methylhydrogen polysiloxane^(f)Replicate samples ^(g)Replicate sample ^(h)LE 46 to be 35% solidsemulsion of polydimethylsiloxane ^(i)TPX5688/AQUA-TRETE BSM40 to be 40%emulsion of alkylsilane ^(j)PGN, a grade of clay, montmorillonite, fromNanocor ^(k)Cloisite NA+, the sodium salt of a clay from Southern ClayProducts ^(l)Blown Soya Emulsion (25%), a 25% solids emulsion of soybeanoil with PEG 400 dioleate (4% on solids) and guar gum (1% on solids)^(m)Bentolite L-10, a clay from Southern Clay Products ^(n)Michem 45745PE Emulsion (50%), a 25% solids emulsion of low molecular weightpolyethylene ^(o)Bone Glue Solution, a 30% solids solution ^(p)AxelINT-26-LF95, a fat-based, mold-release agent/emulsion ^(q)ISO Chill Whey9010 ^(r)Not calculated ^(s)Not measured

TABLE 5 Measured Tensile Strength for Glass Bead Shell BoneCompositions^(a) Prepared With Ammonium Polycarboxylate-Dextrose BinderVariants^(b) vs. Polycarboxylic Acid-based Binders vs. Standard PFBinder Weath- Mean^(c) Mean^(c) ered:Dry Dry Weathered Tensile TensileTensile Strength Strength Strength Binder Description Ratio (psi) (psi)Triammonium citrate-dextrose (1:6)^(d) 0.76^(d) 358^(d)  273^(d)Triammonium citrate-dextrose (1:5) 0.68 377 257 +Sodium carbonate (0.9g) 0.71 341 243 +Sodium carbonate (1.8 g) 0.78 313 243 AQUASET-529 +Dex + Ammonia^(e) 0.41 499 205 AQUASET-529 + Dex + Silane^(f) 0.57 541306 AQUASET-529 + Ammonia + Silane^(g) 0.11 314  33 AQUASET-529 +Silane^(h) 0.48 605 293 PETol + Maleic Acid + Silane^(i) 0.73 654 477PETol + Maleic Acid + TSA + Silane^(j) 0.64 614 390 [Binder^(j) +Ammonia + Dex + Silane]^(k) 0.58 420 245 PETol + Citric Acid +Silane^(l) 0.56 539 303 CRITERION 2000 + Glycerol^(m) 0.26 532 136CRITERION 2000 + Glycerol^(n) 0.20 472  95 SOKALAN + Dex + Ammonia^(o)0.66 664 437 NF1 + Dex + Ammonia^(p) 0.50 877 443 Standard PF(Ductliner) Binder 0.79 637 505 ^(a)From Example 6 ^(b)From Example 5^(c)Mean of nine shell bone samples ^(d)Average of seven differentbatches of triammonium citrate-dextrose (1:6) binder made over afive-month period ^(e)200 g AQUASET-529 + 87 g 19% ammonia + 301 gDextrose + 301 g water to be a 30% solution ^(f)300 mL of solution frombinder^(e) + 0.32 g of SILQUEST A-1101 ^(g)200 g AQUASET-529 + 87 g 19%ammonia + 101 g water + 0.6 g SILQUEST A-1101 ^(h)AQUASET-529 + SILQUESTA-1101 (at 0.5% binder solids), diluted to 30% solids ^(i)136 gpentaerythritol + 98 g maleic anhydride + 130 g water, refluxed for 30minutes; 232 g of resulting solution mixed with 170 g water and 0.6 g ofSILQUEST A-1101 ^(j)136 g pentaerythritol + 98 g maleic anhydride + 130g water + 1.5 mL of 66% p- toluenesulfonic acid, refluxed for 30minutes; 232 g of resulting solution mixed with 170 g water and 0.6 g ofSILQUEST A-1101 ^(k)220 g of binder^(i) + 39 g of 19% ammonia + 135 gDextrose + 97 g water + 0.65 g SILQUEST A-1101 ^(l)128 g of citricacid + 45 g of pentaerythritol + 125 g of water, refluxed for 20minutes; resulting mixture diluted to 30% solids and SILQUEST A-1101added at 0.5% on solids ^(m)200 g of Kemira CRITERION 2000 + 23 gglycerol + 123 g water + 0.5 g SILQUEST A-1101 ^(n)200 g of KemiraCRITERION 2000 + 30 g glycerol + 164 g water + 0.6 g SILQUEST A-1101^(o)100 g of BASF SOKALAN CP 10 S + 57 g 19% ammonia + 198 g Dextrose +180 g water + 0.8 g SILQUEST A-1101 ^(p)211 g of H.B. Fuller NF1 + 93 g19% ammonia + 321 g Dextrose + 222 g water + 1.33 g SILQUEST A-1101

TABLE 6 Measured Tensile Strength for Glass Bead Shell BoneCompositions^(a) Prepared With Ammonium Polycarboxylate-Sugar BinderVariants^(b) vs. Standard PF Binder Mean^(c) Mean^(c) Weathered:Dry DryWeathered Tensile Tensile Tensile Strength Strength Strength BinderDescription Molar Ratio Ratio (psi) (psi) Triammoniumcitrate-Dextrose^(d) Dextrose = 2 × COOH 0.76^(d) 358^(d) 273^(d)Triammonium citrate-DHA^(e) DHA = 2 × COOH 1.02 130 132 Triammoniumcitrate-Xylose Xylose = 2 × COOH 0.75 322 241 Triammoniumcitrate-Fructose Fructose = 2 × COOH 0.79 363 286 Diammoniumtartarate-Dextrose Dextrose = 2 × COOH 0.76 314 239 Diammoniummaleate-Dextrose Dextrose = 2 × COOH 0.78 393 308 Diammoniummaliate-Dextrose Dextrose = 2 × COOH 0.67 49 280 Diammoniumsuccinate-Dextrose Dextrose = 2 × COOH 0.70 400 281 Ammoniumlactate^(f)-Dextrose Dextrose = 2 × COOH 0.68 257 175 Ammonia + tannicacid^(g)-Dextrose Dextrose = 2 × NH₄ ^(+ h) 0.50 395 199 Standard PF(Ductliner) Binder — 0.79 637 505 ^(a)From Example 6 ^(b)From Example 5^(c)Mean of nine shell bone samples ^(d)Average of seven batches ^(e)DHA= dihydroxyacetone ^(f)Monocarboxylate ^(g)Non-carboxylic acid ^(h)pH ≧7

TABLE 7 Measured Tensile Strength and Loss on Ignition for Glass FiberMats^(a) Prepared With Ammonium Polycarboxylate-Sugar (1:6) BinderVariants^(b) vs. Standard PF Binder Weath- Mean^(c) ered:Dry Mean^(c)Dry Weathered Mean Tensile Tensile Tensile % Strength Strength StrengthBinder Composition LOI Ratio (lb force) (lb force) Triammoniumcitrate-Dex^(d) 5.90 0.63 11.4 7.2 Triammonium citrate-Dex 6.69 0.7214.6 10.5 Diammonium maliate-Dex 5.02 0.86 10.2 8.8 Diammoniummaliate-Dex 6.36 0.78 10.6 8.3 Diammonium succinate-Dex 5.12 0.61 8.04.9 Diammonium succinate-Dex 4.97 0.76 7.5 5.7 Triammoniumcitrate-Fruc^(e) 5.80 0.57 11.9 6.8 Triammonium citrate-Fruc 5.96 0.6011.4 6.8 Diammonium maliate-Fruc 6.01 0.60 9.0 5.4 Diammoniummaliate-Fruc 5.74 0.71 7.9 5.6 Diammonium succinate-Fruc 4.60 1.05 3.73.9 Diammonium succinate-Fruc 4.13 0.79 4.4 3.5 Triammoniumcitrate-DHA^(f) 4.45 0.96 4.7 4.5 Triammonium citrate-DHA 4.28 0.74 5.44.0 Triammonium citrate-DHA- 3.75 0.52 8.5 4.4 Glycerol^(g) Triammoniumcitrate-DHA- 3.38 0.59 8.0 4.7 Glycerol^(g) Triammonium citrate-DHA-4.96 0.61 10.7 6.5 PETol^(h) Triammonium citrate-DHA- 5.23 0.65 9.4 6.1PETol^(h) Triammonium citrate-DHA- 5.11 0.74 15.7 11.6 PVOH^(i)Triammonium citrate-DHA- 5.23 0.85 14.9 12.6 PVOH^(i) Standard PFBinder^(j) 7.22 0.75 15.9 12.0 Standard PF Binder^(j) 8.05 0.75 18.814.2 ^(a)From Example 7 ^(b)From Example 5 ^(c)Mean of three glass fibermats ^(d)Dex = Dextrose ^(e)Fruc = Fructose ^(f)DHA = Dihydroxyacetone^(g)Glycerol substituted for 25% of DHA by weight ^(h)PETol =Pentaerythritol substituted for 25% of DHA by weight ^(i)PVOH =Polyvinyl alcohol (86-89% hydrolyzed polyvinyl acetate, MW ~22K-26K),substituted for 20% of DHA by weight ^(j)Ductliner binder

TABLE 8 Testing Results for Cured Blanket from Example 8: Triammoniumcitrate- Dextrose (1:6) Binder vs. Standard PF Binder Melanoidin- PFBinder- Fiberglass Fiberglass BINDER Cured Cured % of Blanket BlanketSTAN- TEST “BINDER” “STANDARD” DARD Density 0.65 0.67 97% Loss onIgnition (%) 13.24% 10.32% 128% Thickness Recovery (dead, 1.46 1.59 92%in.) Thickness Recovery (drop, 1.55 1.64 94% in.) Dust (mg) 8.93 8.80102% Tensile Strength (lb/in. width) Machine Direction 2.77 3.81 73%Cross Machine Dir. 1.93 2.33 83% Avg. 2.35 3.07 76% Parting Strength(g/g) Machine Direction 439.22 511.92 86% Cross Machine Direction 315.95468.99 67% Avg. 377.59 490.46 77% Bond Strength (lb/ft²) 11.58 14.23 81%Water Absorption 1.24% 1.06% 116% (% by weight) Hot Surface PerformancePass Pass — Product Emissions (at 96 Hours) Total VOCs (μg/m³) 0 6 0%Total HCHO (ppm) 0 56 0% Total Aldehydes (ppm) 6 56 11%

TABLE 9 Smoke Development on Ignition for Cured Blanket from Example 8:Triammonium citrate-Dextrose (1:6) Binder vs. Standard PF Binder AverageSEA^(a) External Melanoidin-Fiberglass PF Binder-Fiberglass Heat FluxCured Blanket Cured Blanket 35 kW/m² 2,396 m²/kg 4,923 m²/kg 35 kW/m²1,496 m²/kg 11,488 m²/kg  35 kW/m² 3,738 m²/kg 6,848 m²/kg Overall Avg.= 2,543 m²/kg Overall Avg. = 7,756 m²/kg 50 kW/m² 2,079 m²/kg 7,305m²/kg 50 kW/m² 3,336 m²/kg 6,476 m²/kg 50 kW/m² 1,467 m²/kg 1,156 m²/kgOverall Avg. = 2,294 m²/kg Overall Avg. = 4,979 m²/kg ^(a)SEA = specificextinction area

TABLE 10 Testing Results for Air Duct Board from Example 9: Triammoniumcitrate-Dextrose (1:6) Binder vs. Standard PF Binder PF Binder-Melanoidin- Fiberglass Fiberglass Air Duct BINDER Air Duct Board % ofBoard “STAN- STAN- TEST “BINDER” DARD” DARD Density 4.72 4.66 101% Losson Ignition (%) 18.5% 16.8% 110% Flexural Rigidity (lb in²/in width)Machine Direction 724 837 86% Cross Machine Dir. 550 544 101% Avg. 637691 92% Compressive (psi) Resistance 0.67 0.73 92% at 10% Compressive(psi) Resistance 1.34 1.34 100% at 20% Conditioned Compressive (psi)0.719 0.661 109% Resistance at 10% Conditioned Compressive (psi) 1.311.24 106% Resistance at 20% Compressive Modulus (psi) 6.85 7.02 97%Conditioned Compressive 6.57 6.44 102% Modulus (psi) Product Emissions(at 96 Hours) Total VOCs (μg/m³) 40 39 102% Total HCHO (ppm) 0.007 0.04316% Total Aldehydes (ppm) 0.007 0.043 16%

TABLE 11 Testing Results for R30 Residential Blanket from Example 10:Triammonium citrate-Dextrose (1:6) Binder vs. Standard PF Binder PFBinder ^(a) Binder^(b) Binder^(c) Binder Test (% of Std) (% of Std) (%of Std) Std Thickness recovery (dead, in.): 1 week 10.05 (97%) 10.36(99%) 9.75 (94%) 10.38 6 week 7.17 (91%) 7.45 (94%) 7.28 (92%) 7.90Thickness recovery (drop, in.): 1 week 11.06 (101%) 4.23 (102%) 11.01(100%) 11.00 6 week 9.07 (101%) 9.06 (101%) 9.31 (103%) 8.99 PartingStrength (g/g) Machine Direction 214.62 (78%) 186.80 (68%) 228.22 (83%)275.65 Cross Machine 219.23 (75%) 202.80 (70%) 210.62 (72%) 290.12Direction Average 216.93 (77%) 194.80 (69%) 219.42 (77%) 282.89Durability of Parting Strength (g/g) Machine Direction 214.62 (84%)209.54 (82%) 259.58 (102%) 254.11 Cross Machine 219.23 (87%) 204.12(81%) 221.44 (88%) 252.14 Direction Average 216.93 (86%) 206.83 (82%)240.51 95%) 253.13 Bond Strength (lb/ft2) 1.86 (84%) NM^(d) NM^(d) 2.20Dust (mg) 0.0113 (79%) 0.0137 (96%) 0.0101 (71%) 0.0142 Hot Surface PassPass Pass Pass Performance (pass/fail) Corrosivity (steel) Pass PassPass NM^(d) (pass/fail) ^(a) Melanoidin binder; nominal machinecondition to produce loss on ignition of 5% ^(b)Melanoidin binder;machine adjustment to increase loss on ignition to 6.3% ^(c)Melanoidinbinder; machine adjustment to increase loss on ignition to 6.6% ^(d)Notmeasured

TABLE 12 Testing Results for R19 Residential Blanket from Example 11(Batch A-1): Triammonium citrate-Dextrose (1:6) Binder vs. Standard PFBinder PF Binder- Melanoidin- Fiberglass Fiberglass R19 BINDER R19Residential % of Residential “STAN- STAN- TEST “BINDER” DARD” DARDThickness Recovery (dead, in.): 1 week 6.02 6.05 99% 5 week 6.15 6.6792% 6 week 4.97 5.14 97% 3 month 6.63 6.20 107% Thickness Recovery(drop, in.): 1 week 6.79 6.69 101% 4 week 6.92 7.11 97% 6 week 5.83 6.0796% 3 month 7.27 6.79 107% Dust (mg) 2.88 8.03 36% Tensile Strength(lb/in. width) Machine Direction 2.42 3.47 70% Cross Machine Dir. 2.003.03 66% Average 2.21 3.25 68% Parting Strength (g/g) Machine Direction128.18 173.98 74% Cross Machine Direction 118.75 159.42 74% Average123.47 166.70 74% Durability of Parting Strength (g/g) Machine Direction143.69 161.73 89% Cross Machine Direction 127.30 149.20 85% Average135.50 155.47 87% Bond Strength (lb/ft²) 1.97 2.37 83% Water Absorption(%) 7.1 7.21 98% Hot Surface Performance Pass Pass — Corrosion Pass Pass— Stiffness-Rigidity 49.31 44.94 110%

TABLE 13 Testing Results for R19 Residential Blanket from Example 11:Triammonium citrate-Dextrose (1:6) Binder Variants vs. Standard PFBinder Binder Batch Binder Batch Binder Batch Binder Batch PF A-2^(a)B^(a) C^(a) D^(a) Binder Test (% of Std) (% of Std) (% of Std) (% ofStd) Std. Thickness recovery (dead, in.): 1 week 5.94 (99%) 5.86 (98%)6.09 (101%) 6.25 (104%) 6.01 6 week 4.86 (91%) 5.29 (99%) 5.0 (93%) 5.10(95%) Thickness recovery (drop, in.): 1 week 6.83 (105%) 6.7025 (103%)6.81 (104%) 6.88 (105%) 6.00 6 week 5.76 (96%) 6.02 (100%) 5.89 (98%)6.00 (100%) Tensile Strength (lb/in) Machine Direction 1.28 (36%) 1.40(39%) 1.71 (48%) 1.55 (43%) 3.58 Cross Machine Direction 1.65 (71%) 1.21(52%) 1.12 (48%) 1.12 (48%) 2.31 Average 1.47 (50%) 1.31 (44%) 1.42(48%) 1.34 (45%) 2.95 Parting Strength (g/g) Machine Direction 111.82(42%) 164.73 (62%) 136.00 (51%) 164.56 (62%) 264.81 Cross MachineDirection 140.11 (85%) 127.93 (78%) 126.46 (77%) 108.44 (66%) 164.60Average 125.97 (59%) 146.33 (68%) 131.23 (61%) 136.50 (64%) 214.71Durability of Parting Strength (g/g) Machine Direction 138.55 (72%)745.62 (76%) 113.37 (59%) 176.63 (92%) 191.20 Cross Machine Direction158.17 (104%) 116.44 (77%) 97.10 (64%) 162.81 (107%) 151.49 Average148.36 (86%) 131.03 (76%) 105.24 (61%) 169.72 (99%) 171.35 Bond Strength(lb/ft2) 1.30 (52%) 1.50 (60%) 1.60 (64%) 1.60 (64%) 2.50 Dust (mg)0.0038 (86%) 0.0079 (179%) 0.0053 (120%) 0.0056 (126%) 0.0044Stiffness-Rigidity (degrees) 57.50 (N/A) 55.50 (N/A) 61.44 (N/A) 59.06(N/A) 39.38 ^(a)Melanoidin binder

TABLE 14 GC/MS Analysis of Gaseous Compounds Produced During Pyrolysisof Cured Blanket (from Example 8) Prepared With AmmoniumCitrate-Dextrose (1:6) Binder Retention Time (min) TentativeIdentification % Peak Area 1.15 2-cyclopenten-1-one 10.67 1.342,5-dimethyl-furan 5.84 3.54 furan 2.15 3.60 3-methyl-2,5-furandione3.93 4.07 phenol 0.38 4.89 2,3-dimethyl-2-cyclopenten-1-one 1.24 5.112-methyl phenol 1.19 5.42 4-methyl phenol 2.17 6.46 2,4-dimethyl-phenol1.13 10.57 dimethylphthalate 0.97 17.89 octadecanoic acid 1.00 22.75erucylamide 9.72

TABLE 15 GC/MS Analysis of Gaseous Compounds Produced During ThermalCuring of Pipe Insulation Uncured (from Example 12) Prepared WithAmmonium Citrate-Dextrose (1:6) Binder Retention Time (min)Identification % Peak Area 1.33 2,5-dimethylfuran 1.02 2.25 furfural OR3-furaldehyde 2.61 2.48 2-furanmethanol OR 3- 1.08 furanmethanol 3.131-(2-furanyl)-ethanone 0.52 3.55 furan 4.92 3.622-pyridinecarboxyaldehyde 0.47 3.81 5-methylfurfural 3.01 3.99furancarboxylic acid, methyl ester 0.34 4.88 3,4-dimethyl-2,5-furandione0.53 5.41 2-furancarboxylic acid 1.01 6.372-amino-6-hydroxymethylpyridine 1.08 6.67 6-methyl-3-pyridinol 0.49 7.592-furancarboxaldehyde 0.47 7.98 picolinamide 0.24 10.342H-1-benzopyran-2-one 0.23 16.03 hexadecanoic acid 0.21 17.90octadecanoic acid 2.97 22.74 erucylamide 10.02

While certain embodiments of the present invention have been describedand/or exemplified above, it is contemplated that considerable variationand modification thereof are possible. Accordingly, the presentinvention is not limited to the particular embodiments described and/orexemplified herein.

The invention claimed is:
 1. A method of making a thermal or acousticalinsulation product, wherein the thermal or acoustical insulation productcomprises mineral fibers, said mineral fibers being present in theinsulation product in the range from about 80% to about 99% by weight,wherein the method comprises: providing a collection of mineral fibers;spraying an uncured aqueous binder solution onto the collection ofmineral fibers during production of the insulation product, the aqueousbinder solution comprising: (i) monomeric polycarboxylic acid ammoniumsalt(s) consisting of polycarboxylate ions and ⁺NH₄ ions, (ii) reducingsugar(s), and iii) optionally, ammonia, wherein the percent by dryweight of the reducing sugar(s) with respect to the total weight ofmonomeric polycarboxylic acid ammonium salt(s) and reducing sugar(s) inthe aqueous binder solution ranges from about 70% to about 90%, andwherein the percent by dry weight of the monomeric polycarboxylic acidammonium salt(s) with respect to the total weight of monomericpolycarboxylic acid ammonium salt(s) and reducing sugar(s) in theaqueous binder solution ranges from about 10% to about 30%; transferringthe binder coated collection of mineral fibers to and through a curingoven; heating the binder coated collection of mineral fibers in thecuring oven and curing the binder so as to produce the thermal oracoustical insulation product, wherein the cured binder is aformaldehyde-free, water-resistant, thermoset binder comprisingnitrogen-containing polymers that attach the mineral fibers together. 2.The method of claim 1, wherein the percent by dry weight of the ⁺NH₄ions with respect to the total weight of polycarboxylic acid ammoniumsalt(s) and reducing sugar(s) in the aqueous binder solution ranges fromabout 2% to about 6%.
 3. The method of claim 1, wherein the reducingsugar(s) is selected from the group consisting of one or more ofdextrose, xylose, fructose, and dihydroxyacetone.
 4. The method of claim1, wherein the reducing sugar(s) comprises dextrose.
 5. The method ofclaim 4, wherein the polycarboxylic acid ammonium salt(s) comprisestriammonium citrate.
 6. The method of claim 1, wherein the uncuredaqueous binder solution further comprises a silicon-containing couplingagent.
 7. The method of claim 6, wherein the silicon-containing couplingagent is amino-substituted.
 8. The method of claim 6, wherein thesilicon-containing coupling agent is a silyl ether.
 9. The method ofclaim 1, wherein the uncured aqueous binder solution further comprises acorrosion inhibitor.
 10. The method of claim 9, wherein the corrosioninhibitor is selected from the group consisting of dedusting oil,monoammonium phosphate, sodium metasilicate pentahydrate, melamine,tin(II)oxalate, and a methylhydrogen silicone fluid emulsion.
 11. Themethod of claim 1, wherein binder in contact with the mineral fibers isdehydrated and subsequently cured.
 12. The method of claim 1, whereincuring of the binder generates water-insoluble melanoidins.
 13. Themethod of claim 1, wherein the binder comprises polymers and/oroligomers and wherein curing of the binder comprises chemicallycross-linking the polymers and/or oligomers.
 14. The method of claim 1,wherein curing of the binder includes concurrent, contemporaneous, orsequential production and cross-linking of melanoidins.
 15. The methodof claim 1, wherein the reducing sugar(s) is selected from the groupconsisting of a pentose, a pentose used in combination with otherreducing sugars, xylose, xylose used in combination with other reducingsugars, a hexose, a hexose used in combination with other reducingsugars, dextrose, dextrose used in combination with other reducingsugars, fructose, and fructose used in combination with other reducingsugars.
 16. The method of claim 1, wherein curing of the bindercomprises esterification-mediated cross-linking.
 17. The method of claim1, wherein curing of the binder forms water-insoluble melanoidins. 18.The method of claim 1, wherein the uncured aqueous binder solution assprayed has a pH>7.
 19. The method of claim 1, wherein the thermal oracoustical insulation product has a density of less than 4.5 pounds percubic foot.
 20. The method of claim 1, wherein the binder coatedcollection of mineral fibers resides within the curing oven for a periodof time from about 0.5 minutes to about 3 minutes.
 21. The method ofclaim 1, wherein the curing oven is operated at a temperature over therange from about 350° F. to about 600° F.
 22. The method of claim 1,wherein the cured insulation product has a binder content in the rangeof about 3% to about 7% as determined by loss on ignition (LOI).
 23. Amethod of making a thermal or acoustical insulation product, wherein thethermal or acoustical insulation product comprises mineral fibers, saidmineral fibers being present in the insulation product in the range fromabout 80% to about 99% by weight, wherein the method comprises:providing a collection of mineral fibers; spraying an uncured aqueousbinder solution onto the collection of mineral fibers during productionof the insulation product, the aqueous binder solution comprising:reactants consisting of (i) polycarboxylic acid ammonium salt(s)consisting of polycarboxylate ions and ⁺NH₄ ions, (ii) reducingsugar(s), and iii) optionally, ammonia, transferring the binder coatedcollection of mineral fibers to and through a curing oven; heating thebinder coated collection of mineral fibers in the curing oven and curingthe binder so as to produce the thermal or acoustical insulationproduct, wherein the cured binder is a formaldehyde-free,water-resistant, thermoset binder comprising nitrogen-containingpolymers that attach the mineral fibers together.
 24. The method ofclaim 23, wherein the reducing sugar(s) comprises dextrose.
 25. Themethod of claim 23, wherein the reducing sugar(s) comprises dextrose andfructose.
 26. The method of claim 24, wherein the polycarboxylic acidammonium salt(s) comprises triammonium citrate.
 27. The method of claim23, wherein the percent by dry weight of the reducing sugar(s) withrespect to the total weight of polycarboxylic acid ammonium salt(s) andreducing sugar(s) in the aqueous binder solution ranges from about 70%to about 90%, and wherein the percent by dry weight of thepolycarboxylic acid ammonium salt(s) with respect to the total weight ofpolycarboxylic acid ammonium salt(s) and reducing sugar(s) in theaqueous binder solution ranges from about 10% to about 30%.
 28. Themethod of claim 23, wherein the uncured aqueous binder solution assprayed has a pH>7.